Carboxylate, resist composition and method for producing resist pattern

ABSTRACT

Provided are a carboxylate capable of producing a resist pattern with satisfactory CD uniformity (CDU), and a resist composition. Disclosed are a carboxylate represented by formula (I) and a resist composition: 
     
       
         
         
             
             
         
       
     
     wherein Ar represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, X 1  represents an oxygen atom or a sulfur atom, R 1  represents a halogen atom or a haloalkyl group having 1 to 12 carbon atoms, R 2  represents a halogen atom, a hydroxy group, a haloalkyl group having 1 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms, —CH 2 — included in the haloalkyl group and the alkyl group may be replaced by —O— or —CO—, m1 represents an integer of 1 to 6, m2 represents an integer of 0 to 4, and Z +  represents an organic cation.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to a carboxylate, a resist composition and a method for producing a resist pattern.

Description of the Related Art

JP 2017-219836 A mentions resist compositions comprising carboxylates represented by the following formulas, respectively.

JP 2017-072691 A mentions resist compositions comprising carboxylates represented by the following formulas, respectively.

SUMMARY OF THE INVENTION

The present invention provides a carboxylate forming a resist pattern with CD uniformity (CDU) which is better than that of a resist pattern formed from the resist compositions comprising the salts mentioned above.

The present invention includes the following inventions.

[1] A carboxylate represented by formula (I):

wherein, in formula (I),

Ar represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent,

X¹ represents an oxygen atom or a sulfur atom,

R¹ represents a halogen atom or a haloalkyl group having 1 to 12 carbon atoms,

R² represents a halogen atom, a hydroxy group, a haloalkyl group having 1 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and —CH₂— included in the haloalkyl group and the alkyl group may be replaced by —O— or —CO—,

m1 represents an integer of 1 to 6, and when m1 is 2 or more, a plurality of groups in parentheses may be the same or different from each other,

m2 represents an integer of 0 to 4, and when m2 is 2 or more, a plurality of R² may be the same or different from each other, and Z⁺ represents an organic cation.

[2] The carboxylate according to [1], wherein Ar is an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. [3] The carboxylate according to [1] or [2], wherein X¹ is an oxygen atom. [4] The carboxylate according to any one of [1] to [3], wherein R¹ is an iodine atom, a fluorine atom or a perfluoroalkyl group having 1 to 3 carbon atoms. [5] The carboxylate according to any one of [1] to [4], wherein R² is an iodine atom, a fluorine atom, a hydroxy group, a perfluoroalkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. [6] A resist composition comprising the carboxylate according to any one of [1] to [5], an acid generator and a resin having an acid-labile group. [7] The resist composition according to [6], wherein the acid generator includes a salt represented by formula (B1):

wherein, in formula (B1),

Q^(b1) and Q^(b2) each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms,

L^(b1) represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, —CH₂— included in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—, and a hydrogen atom included in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group,

Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and —CH₂— included in the alicyclic hydrocarbon group may be replaced by —O—, —SO₂— or —CO—, and

Z1⁺ represents an organic cation.

[8] The resist composition according to [6] or [7], wherein the resin having an acid-labile group includes at least one selected from the group consisting of a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2):

wherein, in formula (a1-0), formula (a1-1) and formula (a1-2),

L^(a01), L^(a1) and L^(a2) each independently represent —O— or *—O—(CH₂)_(k1)—CO—O—, k1 represents an integer of 1 to 7, and * represents a bonding site to —CO—,

R^(a01), R^(a4) and R^(a5) each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom,

R^(a02), R^(a03) and R^(a04) each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group obtained by combining these groups,

R^(a6) and R^(a7) each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these groups,

m1 represents an integer of 0 to 14,

n1 represents an integer of 0 to 10, and

n1′ represents an integer of 0 to 3.

[9] The resist composition according to any one of [6] to [8], wherein the resin having an acid-labile group includes a structural unit represented by formula (a2-A):

wherein, in formula (a2-A),

R^(a50) represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom,

R^(a51) represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group,

A^(a50) represents a single bond or *—X^(a51)-(A^(a52)-X^(a52))_(nb)—, and * represents a bonding site to carbon atoms to which —R^(a50) is bonded,

A^(a52) represents an alkanediyl group having 1 to 6 carbon atoms,

X^(a51) and X^(a52) each independently represent —O—, —CO—O— or —O—CO—,

nb represents 0 or 1, and

mb represents an integer of 0 to 4, and when mb is an integer of 2 or more, a plurality of R^(a51) may be the same or different from each other.

[10] A method for producing a resist pattern, which comprises:

(1) a step of applying the resist composition according to any one of [6] to [9] on a substrate,

(2) a step of drying the applied resist composition to form a composition layer,

(3) a step of exposing the composition layer,

(4) a step of heating the exposed composition layer, and

(5) a step of developing the heated composition layer.

It is possible to produce a resist pattern with satisfactory CD uniformity (CDU) by using a resist composition comprising a carboxylate of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In the present specification, “(meth)acrylic monomer” means “at least one of acrylic monomer and methacrylic monomer”. Notations such as “(meth)acrylate” and “(meth)acrylic acid” mean the same thing. In groups mentioned in the present specification, regarding groups capable of having both a linear structure and a branched structure, they may have either the linear or branched structure. When —CH₂— included in the hydrocarbon group or the like is replaced by —O—, —S—, —CO—, or SO₂—, the same examples shall apply for each group. “Combined group” means a group in which two or more exemplified groups are bonded, and valences of those groups may be appropriately changed depending on a bonding form. “derived” or “induced” means that a polymerizable C═C bond included in the molecule becomes a single bond (a —C—C— group) by polymerization. When stereoisomers exist, all stereoisomers are included.

[Carboxylate Represented by Formula (I)]

The carboxylate of the present invention is a carboxylate represented by formula (I) (hereinafter sometimes referred to as “carboxylate (I)” or “salt (I)”).

Of the carboxylate (I), the side having negative charge is sometimes referred to as “anion (I)”, and the side having positive charge is sometimes referred to as “cation (I)”:

wherein all symbols are the same as defined above.

In formula (I), examples of the aromatic hydrocarbon group in Ar include, in the case of divalent, aromatic hydrocarbon groups, for example, arylene groups such as a phenylene group, a naphthylene group, an anthrylene group, a biphenylene group and a phenanthrylene group. Examples thereof include, in the case of trivalent, aromatic hydrocarbon groups such as a benzenetriyl group, a naphthalenetriyl group, an anthracenetriyl group, a biphenyltriyl group and a phenanthrenetriyl group. Examples thereof include, in the case of tetravalent, aromatic hydrocarbon groups such as a benzenetetrayl group, a naphthalenetetrayl group, an anthracenetetrayl group, a biphenyltetrayl group and a phenanthrenetetrayl group. Examples thereof include, in the case of pentavalent, aromatic hydrocarbon groups such as a benzenepentayl group, a naphthalenepentayl group, an anthracenepentayl group, a biphenylpentayl group and a phenanthrenepentayl group. Examples thereof include, in the case of hexavalent, aromatic hydrocarbon groups such as a benzenehexayl group, a naphthalenehexayl group, an anthracenehexayl group, a biphenylhexayl group and a phenanthrenehexayl group.

The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14, still more preferably 6 to 10, and yet more preferably 6.

Examples of the substituent which may be possessed by Ar include a hydroxy group, a carboxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, or groups obtained by combining these groups.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group and the like.

Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group and the like.

The alkoxycarbonyl group having 2 to 13 carbon atoms, the alkylcarbonyl group having 2 to 13 carbon atoms and the alkylcarbonyloxy group having 2 to 13 carbon atoms represent a group in which a carbonyl group or a carbonyloxy group is bonded to the above-mentioned alkyl group or alkoxy group.

Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group and the like, examples of the alkylcarbonyl group having 2 to 13 carbon atoms include an acetyl group, a propionyl group and a butyryl group, and examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include an acetyloxy group, a propionyloxy group, a butyryloxy group and the like.

The substituent is preferably an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a hydroxy group, a carboxy group or a halogen atom, more preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group or a halogen atom, and still more preferably an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a hydroxy group or a halogen atom.

Ar is preferably an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, still more preferably an aromatic hydrocarbon group having 6 carbon atoms which may have a substituent, and yet more preferably a phenylene group which may have a substituent. The substituent is preferably an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a hydroxy group, a carboxy group or a halogen atom, more preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group or a halogen atom, and still more preferably an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a hydroxy group or a halogen atom.

Examples of the halogen atom as for R¹ and R² include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The haloalkyl group having 1 to 12 carbon atoms in R¹ and R² represents an alkyl group having 1 to 12 carbon atoms which has a halogen atom, and examples thereof include an alkyl fluoride group having 1 to 12 carbon atoms, an alkyl chloride group having 1 to 12 carbon atoms, an alkyl bromide group having 1 to 12 carbon atoms, an alkyl iodide group having 1 to 12 carbon atoms and the like. Examples of the haloalkyl group include a perfluoroalkyl group having 1 to 12 carbon atoms (a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, etc.), a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, a 4,4,4-trifluorobutyl group, a 3,3,4,4,4-pentafluorobutyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group and the like. The number of carbon atoms of the haloalkyl group is preferably 1 to 9, more preferably 1 to 6, still more preferably 1 to 4, and yet more preferably 1 to 3.

Examples of the alkyl group having 1 to 12 carbon atoms as for R² include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group and a nonyl group. The number of carbon atoms of the alkyl group is preferably 1 to 9, more preferably 1 to 6, still more preferably 1 to 4, and yet more preferably 1 to 3.

When —CH₂— included in the haloalkyl group or the alkyl group represented by R² is replaced by —O— or —CO—, the number of carbon atoms before replacement is taken as the total number of carbon atoms of the haloalkyl group or the alkyl group. Examples of the replaced group include a hydroxy group (a group in which —CH₂— included in the methyl group is replaced by —O—), a carboxy group (a group in which —CH₂—CH₂— included in the ethyl group is replaced by —O—CO—), an alkoxy group (a group in which —CH₂— at any position included in the alkyl group is replaced by —O—), an alkoxycarbonyl group (a group in which —CH₂—CH₂— at any position included in the alkyl group is replaced by —O—CO—), an alkylcarbonyl group (a group in which —CH₂— at any position included in the alkyl group is replaced by —CO—), an alkylcarbonyloxy group (a group in which —CH₂—CH₂— at any position included in the alkyl group is replaced by —CO—O—), a haloalkoxy group (a group in which —CH₂— at any position included in the haloalkyl group is replaced by —O—), a haloalkoxycarbonyl group (a group in which —CH₂—CH₂— at any position included in the haloalkyl group is replaced by —O—CO—), a haloalkylcarbonyl group (a group in which —CH₂— at any position included in the haloalkyl group is replaced by —CO—), a haloalkylcarbonyloxy group (a group in which —CH₂—CH₂— at any position included in the haloalkyl group is replaced by —CO—O—), and a group obtained by combining two or more of these groups.

Examples of the alkoxy group include alkoxy groups having 1 to 11 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group and the like. The number of carbon atoms of the alkoxy group is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 3.

The alkoxycarbonyl group, the alkylcarbonyl group and the alkylcarbonyloxy group represent a group in which a carbonyl group or a carbonyloxy group is bonded to the above-mentioned alkyl group or alkoxy group.

Examples of the alkoxycarbonyl group include alkoxycarbonyl groups having 2 to 11 carbon atoms, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group and the like; examples of the alkylcarbonyl group include alkylcarbonyl groups having 2 to 12 carbon atoms, for example, an acetyl group, a propionyl group and a butyryl group; and examples of the alkylcarbonyloxy group include alkylcarbonyloxy groups having 2 to 11 carbon atoms, for example, an acetyloxy group, a propionyloxy group, a butyryloxy group and the like. The number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 6, more preferably 2 to 4, and still more preferably 2 or 3. The number of carbon atoms of the alkylcarbonyl group is preferably 2 to 6, more preferably 2 to 4, and still more preferably 2 or 3. The number of carbon atoms of the alkylcarbonyloxy group is preferably 2 to 6, more preferably 2 to 4, and still more preferably 2 or 3.

Examples of the haloalkoxy group, the haloalkoxycarbonyl group, the haloalkylcarbonyl group and the haloalkylcarbonyloxy group include a haloalkoxy group having 1 to 11 carbon atoms, a haloalkoxycarbonyl group having 2 to 11 carbon atoms, a haloalkylcarbonyl group having 2 to 12 carbon atoms and a haloalkylcarbonyloxy group having 2 to 11 carbon atoms, for example, a group in which one or more hydrogen atoms of the above-mentioned groups are replaced by a halogen atom.

X¹ is preferably an oxygen atom.

The bonding site of X¹ to Ar may be any of the o-position, the m-position and the p-position, with respect to the bonding site of COO⁻, when Ar is an aromatic hydrocarbon group having 6 carbon atoms which may have a substituent. Particularly, when m1 is 1, it is preferable that X¹ is bonded at the m-position or the p-position, and more preferable that X¹ is bonded at the p-position, with respect to the bonding site of COO⁻. When m1 is 2, it is preferable that one X¹ is bonded at the o-position or the m-position and one X¹ is bonded at the o-position or the m-position, and more preferable that two X¹ are bonded at the m-position, with respect to the bonding site of COO⁻. When m1 is 3, it is preferable that two X¹ are bonded at the o-position or the m-position and one X¹ is bonded at the p-position or the m-position, and more preferable that two X¹ are bonded at the m-position and one X¹ is bonded at the p-position, with respect to the bonding site of COO⁻. When m1 is 4, it is preferable that two X¹ are bonded at the o-position or the m-position and two X¹ are bonded at the p-position or the m-position, and more preferable that two X¹ are bonded at the o-position and two X¹ are bonded at the m-position, with respect to the bonding site of COO⁻.

m1 is preferably 1, 2, 3, 4 or 5, more preferably 1, 2, 3 or 4, and still more preferably 1, 2 or 4.

m2 is preferably 0, 1, 2 or 4, and more preferably 0, 2 or 4.

R¹ is preferably an iodine atom, a fluorine atom or a haloalkyl group having 1 to 6 carbon atoms, more preferably an iodine atom, a fluorine atom or a perfluoroalkyl group having 1 to 3 carbon atoms, still more preferably an iodine atom, a fluorine atom or a trifluoromethyl group, and yet more preferably an iodine atom or a fluorine atom.

Preferably, R² represents an iodine atom, a fluorine atom, a hydroxy group, a haloalkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms (—CH₂— included in the haloalkyl group and the alkyl group may be replaced by —O— or —CO—), more preferably an iodine atom, a fluorine atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, still more preferably an iodine atom, a fluorine atom, a hydroxy group, a perfluoroalkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and yet more preferably an iodine atom, a fluorine atom, a hydroxy group, a trifluoromethyl group or a methoxy group.

The bonding site of R¹ to the benzene ring may be any of the o-position, the m-position and the p-position, with respect to the bonding site of X¹. Particularly, the bonding site of R¹ to the benzene ring is preferably the m-position or the p-position, with respect to the bonding site of X¹.

The bonding site of R² to the benzene ring may be any of the o-position, the m-position and the p-position, with respect to the bonding site of X¹. Particularly, when m2 is 1, the bonding site of R² to the benzene ring is preferably the m-position or the p-position, with respect to the bonding site of X¹. When m2 is 2, it is preferable that one bonding site is the o-position or the m-position and one bonding site is the o-position or the p-position, with respect to the bonding site of X¹. When m2 is 4, it is preferable that two bonding sites are the o-position or the m-position and two bonding sites are the m-position or the p-position, with respect to the bonding site of X¹.

Examples of the anion (I) include the following anions. Of these, anions represented by formula (Ia-1) to formula (Ia-3), formula (Ia-10) to formula (Ia-18), formula (Ia-25) to formula (Ia-30) and formula (Ia-47) to formula (Ia-54) are preferable.

Examples of the organic cation as for Z⁺ include an organic onium cation, an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation and an organic phosphonium cation. Of these, an organic sulfonium cation and an organic iodonium cation are preferable, and an aryl sulfonium cation is more preferable. Specific examples thereof include a cation represented by any one of formula (b2-1) to formula (b2-4) (hereinafter sometimes referred to as “cation (b2-1)” according to the number of formula).

In formula (b2-1) to formula (b2-4),

R^(b4) to R^(b6) each independently represent a chain hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms or an aromatic hydrocarbon group having 6 to 36 carbon atoms, a hydrogen atom included in the chain hydrocarbon group may be substituted with a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, a hydrogen atom included in the alicyclic hydrocarbon group may be substituted with a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms or a glycidyloxy group, and a hydrogen atom included in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkyl fluoride group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.

R^(b4) and R^(b5) may be bonded to each other to form a ring together with sulfur atoms to which R^(b4) and R^(b5) are bonded, and —CH₂— included in the ring may be replaced by —O—, —S— or —CO—,

R^(b7) and R^(b8) each independently represent a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alkyl fluoride group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms,

m2 and n2 each independently represent an integer of 0 to 5,

when m2 is 2 or more, a plurality of R^(b7) may be the same or different, and when n2 is 2 or more, a plurality of R^(b8) may be the same or different,

R^(b9) and R^(b10) each independently represent a chain hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms,

R^(b9) and R^(b10) may be bonded to each other to form a ring together with sulfur atoms to which R^(b9) and R^(b10) are bonded, and —CH₂— included in the ring may be replaced by —O—, —S— or —CO—,

R^(b11) represents a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms,

R^(b12) represents a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, a hydrogen atom included in the chain hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, a hydrogen atom included in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyloxy group having 1 to 12 carbon atoms,

R^(b11) and R^(b12) may be bonded to each other to form a ring, including —CH—CO— to which R^(b11) and R^(b12) are bonded, and —CH₂— included in the ring may be replaced by —O—, —S— or —CO—,

R^(b13) to R^(b18) each independently represent a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alkyl fluoride group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms,

L^(b31) represents a sulfur atom or an oxygen atom,

o2, p2, s2 and t2 each independently represent an integer of 0 to 5,

q2 and r2 each independently represent an integer of 0 to 4,

u2 represents 0 or 1, and

when o2 is 2 or more, a plurality of R^(b13) are the same or different, when p2 is 2 or more, a plurality of R^(b14) are the same or different, when q2 is 2 or more, a plurality of R^(b15) are the same or different, when r2 is 2 or more, a plurality of R^(b16) are the same or different, when s2 is 2 or more, a plurality of R^(b17) are the same or different, and when t2 is 2 or more, a plurality of R^(b18) are the same or different.

When u2 is 0, any one of o2, p2, q2 and r2 is preferably 1 or more, and at least one of R^(b13) to R^(b16) is preferably a halogen atom, and when u2 is 1, at least one of o2, p2, s2, t2, q2 and r2 is preferably 1 or more, and at least one of R^(b13) to R^(b18) is preferably a halogen atom.

Furthermore, when u2 is 0, r2 is preferably 1 or more, and more preferably 1. When u2 is 0 and r2 is 1 or more, R^(b16) is preferably a halogen atom.

The aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group.

Examples of the chain hydrocarbon group include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group and a 2-ethylhexyl group.

Particularly, the chain hydrocarbon group of R^(b9) to R^(b12) preferably has 1 to 12 carbon atoms.

The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups.

Particularly, the alicyclic hydrocarbon group of R^(b9) to R^(b12) preferably has 3 to 18 carbon atoms, and more preferably 4 to 12 carbon atoms.

Examples of the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-methyladamantan-2-yl group, a 2-ethyladamantan-2-yl group, a 2-isopropyladamantan-2-yl group, a methylnorbornyl group, an isobornyl group and the like. In the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, the total number of carbon atoms of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less.

The alkyl fluoride group represents an alkyl group having 1 to 12 carbon atoms which has a fluorine atom, and examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluorobutyl group and the like. The number of carbon atoms of the alkyl fluoride group is preferably 1 to 9, more preferably 1 to 6, still more preferably 1 to 4.

Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a biphenyl group, a naphthyl group and a phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and examples thereof include an aromatic hydrocarbon group which has a chain hydrocarbon group (a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a p-ethylphenyl group, a p-tert-butylphenyl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, etc.) and an aromatic hydrocarbon group which has an alicyclic hydrocarbon group (a p-cyclohexylphenyl group, a p-adamantylphenyl group, etc.).

When the aromatic hydrocarbon group has a chain hydrocarbon group or an alicyclic hydrocarbon group, a chain hydrocarbon group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms are preferable.

Examples of the aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group and the like.

Examples of the chain hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group and a naphthylethyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and a dodecyloxy group.

Examples of the alkylcarbonyl group include an acetyl group, a propionyl group and a butyryl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, a butylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, a pentylcarbonyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group and a 2-ethylhexylcarbonyloxy group.

The ring formed by bonding R^(b4) and R^(b5) each other, together with sulfur atoms to which R^(b4) and R^(b5) are bonded, may be a monocyclic, polycyclic, aromatic, nonaromatic, saturated or unsaturated ring. This ring includes a ring having 3 to 18 carbon atoms and is preferably a ring having 4 to 18 carbon atoms. The ring containing a sulfur atom includes a 3-membered to 12-membered ring and is preferably a 3-membered to 7-membered ring and includes, for example, the following rings and the like. * represents a bonding site.

The ring formed by combining R^(b9) and R^(b10) together may be a monocyclic, polycyclic, aromatic, nonaromatic, saturated or unsaturated ring. This ring includes a 3-membered to 12-membered ring and is preferably a 3-membered to 7-membered ring. The ring includes, for example, a thiolan-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, a 1,4-oxathian-4-ium ring and the like.

The ring formed by combining R^(b11) and R^(b12) together may be a monocyclic, polycyclic, aromatic, nonaromatic, saturated or unsaturated ring. This ring includes a 3-membered to 12-membered ring and is preferably a 3-membered to 7-membered ring. Examples thereof include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, an oxoadamantane ring and the like.

Of cation (b2-1) to cation (b2-4), a cation (b2-1) is preferable.

Examples of the cation (b2-1) include the following cations.

Examples of the cation (b2-3) include the following cations.

Examples of the cation (b2-4) include the following cations.

The carboxylate (I) is preferably a combination of the above-mentioned anions and cations. These anions and cations can be optionally combined. The carboxylate (I) preferably includes a combination of an anion represented by any one of formula (Ia-1) to formula (Ia-3), formula (Ia-10) to formula (Ia-18), formula (Ia-25) to formula (Ia-30) and formula (Ia-47) to formula (Ia-54) with a cation (b2-1), a cation (b2-2), a cation (b2-3) or a cation (b2-4).

Specific examples of the carboxylate (I) include carboxylates shown in Table 1. In the following table, the respective symbols represent symbols imparted to structures showing the above-mentioned anions and cations. For example, the carboxylate (I-1) means a salt composed of an anion represented by formula (Ia-1) and a cation represented by formula (b2-c-1), and represents the following salt.

TABLE 1 Carboxylate (I) Anion (I) Cation (I) (I-1) (Ia-1) (b2-c-1) (I-2) (Ia-2) (b2-c-1) (I-3) (Ia-3) (b2-c-1) (I-4) (Ia-4) (b2-c-1) (I-5) (Ia-5) (b2-c-1) (I-6) (Ia-6) (b2-c-1) (I-7) (Ia-7) (b2-c-1) (I-8) (Ia-8) (b2-c-1) (I-9) (Ia-9) (b2-c-1) (I-10) (Ia-10) (b2-c-1) (I-11) (Ia-11) (b2-c-1) (I-12) (Ia-12) (b2-c-1) (I-13) (Ia-13) (b2-c-1) (I-14) (Ia-14) (b2-c-1) (I-15) (Ia-15) (b2-c-1) (I-16) (Ia-16) (b2-c-1) (I-17) (Ia-17) (b2-c-1) (I-18) (Ia-18) (b2-c-1) (I-19) (Ia-19) (b2-c-1) (I-20) (Ia-20) (b2-c-1) (I-21) (Ia-21) (b2-c-1) (I-22) (Ia-22) (b2-c-1) (I-23) (Ia-23) (b2-c-1) (I-24) (Ia-24) (b2-c-1) (I-25) (Ia-25) (b2-c-1) (I-26) (Ia-26) (b2-c-1) (I-27) (Ia-27) (b2-c-1) (I-28) (Ia-28) (b2-c-1) (I-29) (Ia-29) (b2-c-1) (I-30) (Ia-30) (b2-c-1) (I-31) (Ia-31) (b2-c-1) (I-32) (Ia-32) (b2-c-1) (I-33) (Ia-33) (b2-c-1) (I-34) (Ia-34) (b2-c-1) (I-35) (Ia-35) (b2-c-1) (I-36) (Ia-36) (b2-c-1) (I-37) (Ia-37) (b2-c-1) (I-38) (Ia-38) (b2-c-1) (I-39) (Ia-1) (b2-c-10) (I-40) (Ia-2) (b2-c-10) (I-41) (Ia-3) (b2-c-10) (I-42) (Ia-4) (b2-c-10) (I-43) (Ia-5) (b2-c-10) (I-44) (Ia-6) (b2-c-10) (I-45) (Ia-7) (b2-c-10) (I-46) (Ia-8) (b2-c-10) (I-47) (Ia-9) (b2-c-10) (I-48) (Ia-10) (b2-c-10) (I-49) (Ia-11) (b2-c-10) (I-50) (Ia-12) (b2-c-10) (I-51) (Ia-13) (b2-c-10) (I-52) (Ia-14) (b2-c-10) (I-53) (Ia-15) (b2-c-10) (I-54) (Ia-16) (b2-c-10) (I-55) (Ia-17) (b2-c-10) (I-56) (Ia-18) (b2-c-10) (I-57) (Ia-19) (b2-c-10) (I-58) (Ia-20) (b2-c-10) (I-59) (Ia-21) (b2-c-10) (I-60) (Ia-22) (b2-c-10) (I-61) (Ia-23) (b2-c-10) (I-62) (Ia-24) (b2-c-10) (I-63) (Ia-25) (b2-c-10) (I-64) (Ia-26) (b2-c-10) (I-65) (Ia-27) (b2-c-10) (I-66) (Ia-28) (b2-c-10) (I-67) (Ia-29) (b2-c-10) (I-68) (Ia-30) (b2-c-10) (I-69) (Ia-31) (b2-c-10) (I-70) (Ia-32) (b2-c-10) (I-71) (Ia-33) (b2-c-10) (I-72) (Ia-34) (b2-c-10) (I-73) (Ia-35) (b2-c-10) (I-74) (Ia-36) (b2-c-10) (I-75) (Ia-37) (b2-c-10) (I-76) (Ia-38) (b2-c-10) (I-77) (Ia-1) (b2-c-14) (I-78) (Ia-2) (b2-c-14) (I-79) (Ia-3) (b2-c-14) (I-80) (Ia-4) (b2-c-14) (I-81) (Ia-5) (b2-c-14) (I-82) (Ia-6) (b2-c-14) (I-83) (Ia-7) (b2-c-14) (I-84) (Ia-8) (b2-c-14) (I-85) (Ia-9) (b2-c-14) (I-86) (Ia-10) (b2-c-14) (I-87) (Ia-11) (b2-c-14) (I-88) (Ia-12) (b2-c-14) (I-89) (Ia-13) (b2-c-14) (I-90) (Ia-14) (b2-c-14) (I-91) (Ia-15) (b2-c-14) (I-92) (Ia-16) (b2-c-14) (I-93) (Ia-17) (b2-c-14) (I-94) (Ia-18) (b2-c-14) (I-95) (Ia-19) (b2-c-14) (I-96) (Ia-20) (b2-c-14) (I-97) (Ia-21) (b2-c-14) (I-98) (Ia-22) (b2-c-14) (I-99) (Ia-23) (b2-c-14) (I-100) (Ia-24) (b2-c-14) (I-101) (Ia-25) (b2-c-14) (I-102) (Ia-26) (b2-c-14) (I-103) (Ia-27) (b2-c-14) (I-104) (Ia-28) (b2-c-14) (I-105) (Ia-29) (b2-c-14) (I-106) (Ia-30) (b2-c-14) (I-107) (Ia-31) (b2-c-14) (I-108) (Ia-32) (b2-c-14) (I-109) (Ia-33) (b2-c-14) (I-110) (Ia-34) (b2-c-14) (I-111) (Ia-35) (b2-c-14) (I-112) (Ia-36) (b2-c-14) (I-113) (Ia-37) (b2-c-14) (I-114) (Ia-38) (b2-c-14) (I-115) (Ia-1) (b2-c-17) (I-116) (Ia-2) (b2-c-17) (I-117) (Ia-3) (b2-c-17) (I-118) (Ia-4) (b2-c-17) (I-119) (Ia-5) (b2-c-17) (I-120) (Ia-6) (b2-c-17) (I-121) (Ia-7) (b2-c-17) (I-122) (Ia-8) (b2-c-17) (I-123) (Ia-9) (b2-c-17) (I-124) (Ia-10) (b2-c-17) (I-125) (Ia-11) (b2-c-17) (I-126) (Ia-12) (b2-c-17) (I-127) (Ia-13) (b2-c-17) (I-128) (Ia-14) (b2-c-17) (I-129) (Ia-15) (b2-c-17) (I-130) (Ia-16) (b2-c-17) (I-131) (Ia-17) (b2-c-17) (I-132) (Ia-18) (b2-c-17) (I-133) (Ia-19) (b2-c-17) (I-134) (Ia-20) (b2-c-17) (I-135) (Ia-21) (b2-c-17) (I-136) (Ia-22) (b2-c-17) (I-137) (Ia-23) (b2-c-17) (I-138) (Ia-24) (b2-c-17) (I-139) (Ia-25) (b2-c-17) (I-140) (Ia-26) (b2-c-17) (I-141) (Ia-27) (b2-c-17) (I-142) (Ia-28) (b2-c-17) (I-143) (Ia-29) (b2-c-17) (I-144) (Ia-30) (b2-c-17) (I-145) (Ia-31) (b2-c-17) (I-146) (Ia-32) (b2-c-17) (I-147) (Ia-33) (b2-c-17) (I-148) (Ia-34) (b2-c-17) (I-143) (Ia-35) (b2-c-17) (I-150) (Ia-36) (b2-c-17) (I-151) (Ia-37) (b2-c-17) (I-152) (Ia-38) (b2-c-17) (I-153) (Ia-1) (b2-c-18) (I-154) (Ia-2) (b2-c-18) (I-155) (Ia-3) (b2-c-18) (I-156) (Ia-4) (b2-c-18) (I-157) (Ia-5) (b2-c-18) (1-158) (Ia-6) (b2-c-18) (I-159) (Ia-7) (b2-c-18) (I-160) (Ia-8) (b2-c-18) (I-161) (Ia-9) (b2-c-18) (I-162) (Ia-10) (b2-c-18) (I-163) (Ia-11) (b2-c-18) (I-164) (Ia-12) (b2-c-18) (I-165) (Ia-13) (b2-c-18) (I-166) (Ia-14) (b2-c-18) (I-167) (Ia-15) (b2-c-18) (I-168) (Ia-16) (b2-c-18) (I-169) (Ia-17) (b2-c-18) (I-170) (Ia-18) (b2-c-18) (I-171) (Ia-19) (b2-c-18) (I-172) (Ia-20) (b2-c-18) (I-173) (Ia-21) (b2-c-18) (I-174) (Ia-22) (b2-c-18) (I-175) (Ia-23) (b2-c-18) (I-176) (Ia-24) (b2-c-18) (I-177) (Ia-25) (b2-c-18) (I-178) (Ia-26) (b2-c-18) (I-179) (Ia-27) (b2-c-18) (I-180) (Ia-28) (b2-c-18) (I-181) (Ia-29) (b2-c-18) (I-182) (Ia-30) (b2-c-18) (I-183) (Ia-31) (b2-c-18) (I-184) (Ia-32) (b2-c-18) (I-185) (Ia-33) (b2-c-18) (I-186) (Ia-34) (b2-c-18) (I-187) (Ia-35) (b2-c-18) (I-188) (Ia-36) (b2-c-18) (I-189) (Ia-37) (b2-c-18) (I-190) (Ia-38) (b2-c-18) (I-191) (Ia-1) (b2-c-19) (I-192) (Ia-2) (b2-c-19) (I-193) (Ia-3) (b2-c-19) (I-194) (Ia-4) (b2-c-19) (I-195) (Ia-5) (b2-c-19) (I-196) (Ia-6) (b2-c-19) (I-197) (Ia-7) (b2-c-19) (I-198) (Ia-8) (b2-c-19) (I-199) (Ia-9) (b2-c-19) (I-200) (Ia-10) (b2-c-19) (I-201) (Ia-11) (b2-c-19) (I-202) (Ia-12) (b2-c-19) (I-203) (Ia-13) (b2-c-19) (I-204) (Ia-14) (b2-c-19) (I-205) (Ia-15) (b2-c-19) (I-206) (Ia-16) (b2-c-19) (I-207) (Ia-17) (b2-c-19) (I-208) (Ia-18) (b2-c-19) (I-209) (Ia-19) (b2-c-19) (I-210) (Ia-20) (b2-c-19) (I-211) (Ia-21) (b2-c-19) (I-212) (Ia-22) (b2-c-19) (I-213) (Ia-23) (b2-c-19) (I-214) (Ia-24) (b2-c-19) (I-215) (Ia-25) (b2-c-19) (I-216) (Ia-26) (b2-c-19) (I-217) (Ia-27) (b2-c-19) (I-218) (Ia-28) (b2-c-19) (I-219) (Ia-29) (b2-c-19) (I-220) (Ia-30) (b2-c-19) (I-221) (Ia-31) (b2-c-19) (I-222) (Ia-32) (b2-c-19) (I-223) (Ia-33) (b2-c-19) (I-224) (Ia-34) (b2-c-19) (I-225) (Ia-35) (b2-c-19) (I-226) (Ia-36) (b2-c-19) (I-227) (Ia-37) (b2-c-19) (I-228) (Ia-38) (b2-c-19) (I-229) (Ia-1) (b2-c-2 0) (I-230) (Ia-2) (b2-c-20) (I-231) (Ia-3) (b2-c-20) (I-232) (Ia-4) (b2-c-20) (I-233) (Ia-5) (b2-c-20) (I-234) (Ia-6) (b2-c-20) (I-235) (Ia-7) (b2-c-20) (I-236) (Ia-8) (b2-c-20) (I-237) (Ia-9) (b2-c-20) (I-238) (Ia-10) (b2-c-20) (I-239) (Ia-11) (b2-c-20) (I-240) (Ia-12) (b2-c-20) (I-241) (Ia-13) (b2-c-20) (I-242) (Ia-14) (b2-c-20) (I-243) (Ia-15) (b2-c-20) (I-244) (Ia-16) (b2-c-20) (I-245) (Ia-17) (b2-c-20) (I-246) (Ia-18) (b2-c-20) (I-247) (Ia-19) (b2-c-20) (I-248) (Ia-20) (b2-c-20) (I-249) (Ia-21) (b2-c-20) (I-250) (Ia-22) (b2-c-20) (I-251) (Ia-23) (b2-c-20) (I-252) (Ia-24) (b2-c-20) (I-253) (Ia-25) (b2-c-20) (I-254) (Ia-26) (b2-c-20) (I-255) (Ia-27) (b2-c-20) (I-256) (Ia-28) (b2-c-20) (I-257) (Ia-29) (b2-c-20) (I-258) (Ia-30) (b2-c-20) (I-259) (Ia-31) (b2-c-20) (I-260) (Ia-32) (b2-c-20) (I-261) (Ia-33) (b2-c-20) (I-262) (Ia-34) (b2-c-20) (I-263) (Ia-35) (b2-c-20) (I-264) (Ia-36) (b2-c-20) (I-265) (Ia-37) (b2-c-20) (I-266) (Ia-38) (b2-c-20) (I-267) (Ia-1) (b2-c-27) (I-268) (Ia-2) (b2-c-27) (I-269) (Ia-3) (b2-c-27) (I-270) (Ia-4) (b2-c-27) (I-271) (Ia-5) (b2-c-27) (I-272) (Ia-6) (b2-c-27) (I-273) (Ia-7) (b2-c-27) (I-274) (Ia-8) (b2-c-27) (I-275) (Ia-9) (b2-c-27) (I-276) (Ia-10) (b2-c-27) (I-277) (Ia-11) (b2-c-27) (I-278) (Ia-12) (b2-c-27) (I-279) (Ia-13) (b2-c-27) (I-280) (Ia-14) (b2-c-27) (I-281) (Ia-15) (b2-c-27) (I-282) (Ia-16) (b2-c-27) (I-283) (Ia-17) (b2-c-27) (I-284) (Ia-18) (b2-c-27) (I-285) (Ia-19) (b2-c-27) (I-286) (Ia-20) (b2-c-27) (I-287) (Ia-21) (b2-c-27) (I-288) (Ia-22) (b2-c-27) (I-289) (Ia-23) (b2-c-27) (I-290) (Ia-24) (b2-c-27) (I-291) (Ia-25) (b2-c-27) (I-292) (Ia-26) (b2-c-27) (I-293) (Ia-27) (b2-c-27) (I-294) (Ia-28) (b2-c-27) (I-295) (Ia-29) (b2-c-27) (I-296) (Ia-30) (b2-c-27) (I-297) (Ia-31) (b2-c-27) (I-298) (Ia-32) (b2-c-27) (I-299) (Ia-33) (b2-c-27) (I-300) (Ia-34) (b2-c-27) (I-301) (Ia-35) (b2-c-27) (I-302) (Ia-36) (b2-c-27) (I-303) (Ia-37) (b2-c-27) (I-304) (Ia-38) (b2-c-27) (I-305) (Ia-1) (b2-c-30) (I-306) (Ia-2) (b2-c-30) (I-307) (Ia-3) (b2-c-30) (I-308) (Ia-4) (b2-c-30) (I-309) (Ia-5) (b2-c-30) (I-310) (Ia-6) (b2-c-30) (I-311) (Ia-7) (b2-c-30) (I-312) (Ia-8) (b2-c-30) (I-313) (Ia-9) (b2-c-30) (I-314) (Ia-10) (b2-c-30) (I-315) (Ia-11) (b2-c-30) (I-316) (Ia-12) (b2-c-30) (I-317) (Ia-13) (b2-c-30) (I-318) (Ia-14) (b2-c-30) (I-319) (Ia-15) (b2-c-30) (I-320) (Ia-16) (b2-c-30) (I-321) (Ia-17) (b2-c-30) (I-322) (Ia-18) (b2-c-30) (I-323) (Ia-19) (b2-c-30) (I-324) (Ia-20) (b2-c-30) (I-325) (Ia-21) (b2-c-30) (I-326) (Ia-22) (b2-c-30) (I-327) (Ia-23) (b2-c-30) (I-328) (Ia-24) (b2-c-30) (I-329) (Ia-25) (b2-c-30) (I-330) (Ia-26) (b2-c-30) (I-331) (Ia-27) (b2-c-30) (I-332) (Ia-28) (b2-c-30) (I-333) (Ia-29) (b2-c-30) (I-334) (Ia-30) (b2-c-30) (I-335) (Ia-31) (b2-c-30) (I-336) (Ia-32) (b2-c-30) (I-337) (Ia-33) (b2-c-30) (I-338) (Ia-34) (b2-c-30) (I-339) (Ia-35) (b2-c-30) (I-340) (Ia-36) (b2-c-30) (I-341) (Ia-37) (b2-c-30) (I-342) (Ia-38) (b2-c-30) (I-343) (Ia-1) (b2-c-31) (I-344) (Ia-2) (b2-c-31) (I-345) (Ia-3) (b2-c-31) (I-346) (Ia-4) (b2-c-31) (I-347) (Ia-5) (b2-c-31) (I-348) (Ia-6) (b2-c-31) (I-349) (Ia-7) (b2-c-31) (I-350) (Ia-8) (b2-c-31) (I-351) (Ia-9) (b2-c-31) (I-352) (Ia-10) (b2-c-31) (I-353) (Ia-11) (b2-c-31) (I-354) (Ia-12) (b2-c-31) (I-355) (Ia-13) (b2-c-31) (I-356) (Ia-14) (b2-c-31) (I-357) (Ia-15) (b2-c-31) (I-358) (Ia-16) (b2-c-31) (I-359) (Ia-17) (b2-c-31) (I-360) (Ia-18) (b2-c-31) (I-361) (Ia-19) (b2-c-31) (I-362) (Ia-20) (b2-c-31) (I-363) (Ia-21) (b2-c-31) (I-364) (Ia-22) (b2-c-31) (I-365) (Ia-23) (b2-c-31) (I-366) (Ia-24) (b2-c-31) (I-367) (Ia-25) (b2-c-31) (I-368) (Ia-26) (b2-c-31) (I-369) (Ia-27) (b2-c-31) (I-370) (Ia-28) (b2-c-31) (I-371) (Ia-29) (b2-c-31) (I-372) (Ia-30) (b2-c-31) (I-373) (Ia-31) (b2-c-31) (I-374) (Ia-32) (b2-c-31) (I-375) (Ia-33) (b2-c-31) (I-376) (Ia-34) (b2-c-31) (I-377) (Ia-35) (b2-c-31) (I-378) (Ia-36) (b2-c-31) (I-379) (Ia-37) (b2-c-31) (I-380) (Ia-38) (b2-c-31) (I-381) (Ia-39) (b2-c-1) (I-382) (Ia-40) (b2-c-1) (I-383) (Ia-41) (b2-c-1) (I-384) (Ia-42) (b2-c-1) (I-385) (Ia-43) (b2-c-1) (I-386) (Ia-44) (b2-c-1) (I-387) (Ia-45) (b2-c-1) (I-388) (Ia-46) (b2-c-1) (I-389) (Ia-47) (b2-c-1) (I-390) (Ia-48) (b2-c-1) (I-391) (Ia-49) (b2-c-1) (I-392) 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(Ia-47) (b2-c-19) (I-470) (Ia-48) (b2-c-19) (I-471) (Ia-49) (b2-c-19) (I-472) (Ia-50) (b2-c-19) (I-473) (Ia-51) (b2-c-19) (I-474) (Ia-52) (b2-c-19) (I-475) (Ia-53) (b2-c-19) (I-476) (Ia-54) (b2-c-19) (I-477) (Ia-39) (b2-c-20) (I-478) (Ia-40) (b2-c-20) (I-479) (Ia-41) (b2-c-20) (I-480) (Ia-42) (b2-c-20) (I-481) (Ia-43) (b2-c-20) (I-482) (Ia-44) (b2-c-20) (I-483) (Ia-45) (b2-c-20) (I-484) (Ia-46) (b2-c-20) (I-485) (Ia-47) (b2-c-20) (I-486) (Ia-48) (b2-c-20) (I-487) (Ia-49) (b2-c-20) (I-488) (Ia-50) (b2-c-20) (I-489) (Ia-51) (b2-c-20) (I-490) (Ia-52) (b2-c-20) (I-491) (Ia-53) (b2-c-20) (I-492) (Ia-54) (b2-c-20) (I-493) (Ia-39) (b2-c-27) (I-494) (Ia-40) (b2-c-27) (I-495) (Ia-41) (b2-c-27) (I-496) (Ia-42) (b2-c-27) (I-497) (Ia-43) (b2-c-27) (I-498) (Ia-44) (b2-c-27) (I-499) (Ia-45) (b2-c-27) (I-500) (Ia-46) (b2-c-27) (I-501) (Ia-47) (b2-c-27) (I-502) (Ia-48) (b2-c-27) (I-503) (Ia-49) (b2-c-27) (I-504) (Ia-50) (b2-c-27) (I-505) (Ia-51) (b2-c-27) (I-506) (Ia-52) (b2-c-27) (I-507) (Ia-53) 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(b2-c-47) (I-585) (Ia-45) (b2-c-47) (I-586) (Ia-46) (b2-c-47) (I-587) (Ia-47) (b2-c-47) (I-588) (Ia-48) (b2-c-47) (I-583) (Ia-49) (b2-c-47) (I-590) (Ia-50) (b2-c-47) (I-591) (Ia-51) (b2-c-47) (I-592) (Ia-52) (b2-c-47) (I-593) (Ia-53) (b2-c-47) (I-594) (Ia-54) (b2-c-47) (I-595) (Ia-1) (b2-c-48) (I-596) (Ia-2) (b2-c-48) (I-597) (Ia-3) (b2-c-48) (I-598) (Ia-4) (b2-c-48) (I-599) (Ia-5) (b2-c-48) (I-600) (Ia-6) (b2-c-48) (I-601) (Ia-7) (b2-c-48) (I-602) (Ia-8) (b2-c-48) (I-603) (Ia-9) (b2-c-48) (I-604) (Ia-10) (b2-c-48) (I-605) (Ia-11) (b2-c-48) (I-606) (Ia-12) (b2-c-48) (I-607) (Ia-13) (b2-c-48) (I-608) (Ia-14) (b2-c-48) (I-609) (Ia-15) (b2-c-48) (I-610) (Ia-16) (b2-c-48) (I-611) (Ia-17) (b2-c-48) (I-612) (Ia-18) (b2-c-48) (I-613) (Ia-19) (b2-c-48) (I-614) (Ia-20) (b2-c-48) (I-615) (Ia-21) (b2-c-48) (I-616) (Ia-22) (b2-c-48) (I-617) (Ia-23) (b2-c-48) (I-618) (Ia-24) (b2-c-48) (I-619) (Ia-25) (b2-c-48) (I-620) (Ia-26) (b2-c-48) (I-621) (Ia-27) (b2-c-48) (I-622) (Ia-28) (b2-c-48) (I-623) (Ia-29) (b2-c-48) (I-624) (Ia-30) (b2-c-48) (I-625) (Ia-31) (b2-c-48) (I-626) (Ia-32) (b2-c-48) (I-627) (Ia-33) (b2-c-48) (I-628) (Ia-34) (b2-c-48) (I-629) (Ia-35) (b2-c-48) (I-630) (Ia-36) (b2-c-48) (I-631) (Ia-37) (b2-c-48) (I-632) (Ia-38) (b2-c-48) (I-633) (Ia-39) (b2-c-48) (I-634) (Ia-40) (b2-c-48) (I-635) (Ia-41) (b2-c-48) (I-636) (Ia-42) (b2-c-48) (I-637) (Ia-43) (b2-c-48) (I-638) (Ia-44) (b2-c-48) (I-639) (Ia-45) (b2-c-48) (I-640) (Ia-46) (b2-c-48) (I-641) (Ia-47) (b2-c-48) (I-642) (Ia-48) (b2-c-48) (I-643) (Ia-49) (b2-c-48) (I-644) (Ia-50) (b2-c-48) (I-645) (Ia-51) (b2-c-48) (I-646) (Ia-52) (b2-c-48) (I-647) (Ia-53) (b2-c-48) (I-648) (Ia-54) (b2-c-48) (I-649) (Ia-1) (b2-c-51) (I-650) (Ia-2) (b2-c-51) (I-651) (Ia-3) (b2-c-51) (I-652) (Ia-4) (b2-c-51) (I-653) (Ia-5) (b2-c-51) (I-654) (Ia-6) (b2-c-51) (I-655) (Ia-7) (b2-c-51) (I-656) (Ia-8) (b2-c-51) (I-657) (Ia-9) (b2-c-51) (I-658) (Ia-10) (b2-c-51) (I-659) (Ia-11) (b2-c-51) (I-660) (Ia-12) (b2-c-51) (I-661) (Ia-13) (b2-c-51) (I-662) (Ia-14) (b2-c-51) (I-663) (Ia-15) (b2-c-51) (I-664) (Ia-16) (b2-c-51) (I-665) (Ia-17) (b2-c-51) (I-666) (Ia-18) (b2-c-51) (I-667) (Ia-19) (b2-c-51) (I-668) (Ia-20) (b2-c-51) (I-669) (Ia-21) (b2-c-51) (I-670) (Ia-22) (b2-c-51) (I-671) (Ia-23) (b2-c-51) (I-672) (Ia-24) (b2-c-51) (I-673) (Ia-25) (b2-c-51) (I-674) (Ia-26) (b2-c-51) (I-675) (Ia-27) (b2-c-51) (I-676) (Ia-28) (b2-c-51) (I-677) (Ia-29) (b2-c-51) (I-678) (Ia-30) (b2-c-51) (I-679) (Ia-31) (b2-c-51) (I-680) (Ia-32) (b2-c-51) (I-681) (Ia-33) (b2-c-51) (I-682) (Ia-34) (b2-c-51) (I-683) (Ia-35) (b2-c-51) (I-684) (Ia-36) (b2-c-51) (I-685) (Ia-37) (b2-c-51) (I-686) (Ia-38) (b2-c-51) (I-687) (Ia-39) (b2-c-51) (I-688) (Ia-40) (b2-c-51) (I-689) (Ia-41) (b2-c-51) (I-690) (Ia-42) (b2-c-51) (I-691) (Ia-43) (b2-c-51) (I-692) (Ia-44) (b2-c-51) (I-693) (Ia-45) (b2-c-51) (I-694) (Ia-46) (b2-c-51) (I-695) (Ia-47) (b2-c-51) (I-696) (Ia-48) (b2-c-51) (I-697) (Ia-49) (b2-c-51) (I-698) (Ia-50) (b2-c-51) (I-699) (Ia-51) (b2-c-51) (I-700) (Ia-52) (b2-c-51) (I-701) (Ia-53) (b2-c-51) (I-702) (Ia-54) (b2-c-51) (I-703) (Ia-1) (b2-c-54) (I-704) (Ia-2) (b2-c-54) (I-705) (Ia-3) (b2-c-54) (I-706) (Ia-4) (b2-c-54) (I-707) (Ia-5) (b2-c-54) (I-708) (Ia-6) (b2-c-54) (I-709) (Ia-7) (b2-c-54) (I-710) (Ia-8) (b2-c-54) (I-711) (Ia-9) (b2-c-54) (I-712) (Ia-10) (b2-c-54) (I-713) (Ia-11) (b2-c-54) (I-714) (Ia-12) (b2-c-54) (I-715) (Ia-13) (b2-c-54) (I-716) (Ia-14) (b2-c-54) (I-717) (Ia-15) (b2-c-54) (I-718) (Ia-16) (b2-c-54) (I-719) (Ia-17) (b2-c-54) (I-720) (Ia-18) (b2-c-54) (I-721) (Ia-19) (b2-c-54) (I-722) (Ia-20) (b2-c-54) (I-723) (Ia-21) (b2-c-54) (I-724) (Ia-22) (b2-c-54) (I-725) (Ia-23) (b2-c-54) (I-726) (Ia-24) (b2-c-54) (I-727) (Ia-25) (b2-c-54) (I-728) (Ia-26) (b2-c-54) (I-729) (Ia-27) (b2-c-54) (I-730) (Ia-28) (b2-c-54) (I-731) (Ia-29) (b2-c-54) (I-732) (Ia-30) (b2-c-54) (I-733) (Ia-31) (b2-c-54) (I-734) (Ia-32) (b2-c-54) (I-735) (Ia-33) (b2-c-54) (I-736) (Ia-34) (b2-c-54) (I-737) (Ia-35) (b2-c-54) (I-738) (Ia-36) (b2-c-54) (I-739) (Ia-37) (b2-c-54) (I-740) (Ia-38) (b2-c-54) (I-741) (Ia-39) (b2-c-54) (I-742) (Ia-40) (b2-c-54) (I-743) (Ia-41) (b2-c-54) (I-744) (Ia-42) (b2-c-54) (I-745) (Ia-43) (b2-c-54) (I-746) (Ia-44) (b2-c-54) (I-747) (Ia-45) (b2-c-54) (I-748) (Ia-46) (b2-c-54) (I-749) (Ia-47) (b2-c-54) (I-750) (Ia-48) (b2-c-54) (I-751) (Ia-49) (b2-c-54) (I-752) (Ia-50) (b2-c-54) (I-753) (Ia-51) (b2-c-54) (I-754) (Ia-52) (b2-c-54) (I-755) (Ia-53) (b2-c-54) (I-756) (Ia-54) (b2-c-54) (I-757) (Ia-55) (b2-c-1) (I-758) (Ia-56) (b2-c-1) (I-759) (Ia-57) (b2-c-1) (I-760) (Ia-58) (b2-c-1) (I-761) (Ia-59) (b2-c-1) (I-762) (Ia-60) (b2-c-1) (I-763) (Ia-61) (b2-c-1) (I-764) (Ia-62) (b2-c-1) (I-765) (Ia-55) (b2-c-10) (I-766) (Ia-56) (b2-c-10) (I-767) (Ia-57) (b2-c-10) (I-768) (Ia-58) (b2-c-10) (I-769) (Ia-59) (b2-c-10) (I-770) (Ia-60) (b2-c-10) (I-771) (Ia-61) (b2-c-10) (I-772) (Ia-62) (b2-c-10) (I-773) (Ia-55) (b2-c-14) (I-774) (Ia-56) (b2-c-14) (I-775) (Ia-57) (b2-c-14) (I-776) (Ia-58) (b2-c-14) (I-777) (Ia-59) (b2-c-14) (I-778) (Ia-60) (b2-c-14) (I-779) (Ia-61) (b2-c-14) (I-780) (Ia-62) (b2-c-14) (I-781) (Ia-55) (b2-c-17) (I-782) (Ia-56) (b2-c-17) (I-783) (Ia-57) (b2-c-17) (I-784) (Ia-58) (b2-c-17) (I-785) (Ia-59) (b2-c-17) (I-786) (Ia-60) (b2-c-17) (I-787) (Ia-61) (b2-c-17) (I-788) (Ia-62) (b2-c-17) (I-789) (Ia-55) (b2-c-18) (I-790) (Ia-56) (b2-c-18) (I-791) (Ia-57) (b2-c-18) (I-792) (Ia-58) (b2-c-18) (I-793) (Ia-59) (b2-c-18) (I-794) (Ia-60) (b2-c-18) (I-795) (Ia-61) (b2-c-18) (I-796) (Ia-62) (b2-c-18) (I-797) (Ia-55) (b2-c-19) (I-798) (Ia-56) (b2-c-19) (I-799) (Ia-57) (b2-c-19) (I-800) (Ia-58) (b2-c-19) (I-801) (Ia-59) (b2-c-19) (I-802) (Ia-60) (b2-c-19) (I-803) (Ia-61) (b2-c-19) (I-804) (Ia-62) (b2-c-19) (I-805) (Ia-55) (b2-c-20) (I-806) (Ia-56) (b2-c-20) (I-807) (Ia-57) (b2-c-20) (I-808) (Ia-58) (b2-c-20) (I-809) (Ia-59) (b2-c-20) (I-810) (Ia-60) (b2-c-20) (I-811) (Ia-61) (b2-c-20) (I-812) (Ia-62) (b2-c-20) (I-813) (Ia-55) (b2-c-27) (I-814) (Ia-56) (b2-c-27) (I-815) (Ia-57) (b2-c-27) (I-816) (Ia-58) (b2-c-27) (I-817) (Ia-59) (b2-c-27) (I-818) (Ia-60) (b2-c-27) (I-819) (Ia-61) (b2-c-27) (I-820) (Ia-62) (b2-c-27) (I-821) (Ia-55) (b2-c-30) (I-822) (Ia-56) (b2-c-30) (I-823) (Ia-57) (b2-c-30) (I-824) (Ia-58) (b2-c-30) (I-825) (Ia-59) (b2-c-30) (I-826) (Ia-60) (b2-c-30) (I-827) (Ia-61) (b2-c-30) (I-828) (Ia-62) (b2-c-30) (I-829) (Ia-55) (b2-c-31) (I-830) (Ia-56) (b2-c-31) (I-831) (Ia-57) (b2-c-31) (I-832) (Ia-58) (b2-c-31) (I-833) (Ia-59) (b2-c-31) (I-834) (Ia-60) (b2-c-31) (I-835) (Ia-61) (b2-c-31) (I-836) (Ia-62) (b2-c-31) (I-837) (Ia-55) (b2-c-47) (I-838) (Ia-56) (b2-c-47) (I-839) (Ia-57) (b2-c-47) (I-840) (Ia-58) (b2-c-47) (I-841) (Ia-59) (b2-c-47) (I-842) (Ia-60) (b2-c-47) (I-843) (Ia-61) (b2-c-47) (I-844) (Ia-62) (b2-c-47) (I-845) (Ia-55) (b2-c-48) (I-846) (Ia-56) (b2-c-48) (I-847) (Ia-57) (b2-c-48) (I-848) (Ia-58) (b2-c-48) (I-849) (Ia-59) (b2-c-48) (I-850) (Ia-60) (b2-c-48) (I-851) (Ia-61) (b2-c-48) (I-852) (Ia-62) (b2-c-48) (I-853) (Ia-55) (b2-c-51) (I-854) (Ia-56) (b2-c-51) (I-855) (Ia-57) (b2-c-51) (I-856) (Ia-58) (b2-c-51) (I-857) (Ia-59) (b2-c-51) (I-858) (Ia-60) (b2-c-51) (I-859) (Ia-61) (b2-c-51) (I-860) (Ia-62) (b2-c-51) (I-861) (Ia-55) (b2-c-54) (I-862) (Ia-56) (b2-c-54) (I-863) (Ia-67) (b2-c-54) (I-864) (Ia-58) (b2-c-54) (I-865) (Ia-59) (b2-c-54) (I-866) (Ia-60) (b2-c-54) (I-867) (Ia-61) (b2-c-54) (I-868) (Ia-62) (b2-c-54)

Of these, the carboxylate (I) is preferably carboxylate (I-1) to carboxylate (I-3), carboxylate (I-10) to carboxylate (I-18), carboxylate (I-25) to carboxylate (I-30), carboxylate (I-39) to carboxylate (I-41), carboxylate (I-48) to carboxylate (I-56), carboxylate (I-63) to carboxylate (I-68), carboxylate (I-77) to carboxylate (I-79), carboxylate (I-86) to carboxylate (I-94), carboxylate (I-101) to carboxylate (I-106), carboxylate (I-115) to carboxylate (I-117), carboxylate (I-124) to carboxylate (I-132), carboxylate (I-139) to carboxylate (I-144), carboxylate (I-153) to carboxylate (I-155), carboxylate (I-162) to carboxylate (I-170), carboxylate (I-177) to carboxylate (I-182), carboxylate (1-191) to carboxylate (I-193), carboxylate (I-200) to carboxylate (I-208), carboxylate (I-215) to carboxylate (I-220), carboxylate (I-229) to carboxylate (I-231), carboxylate (I-238) to carboxylate (I-246), carboxylate (I-253) to carboxylate (I-258), carboxylate (I-267) to carboxylate (I-269), carboxylate (I-276) to carboxylate (I-284), carboxylate (I-291) to carboxylate (I-296), carboxylate (I-305) to carboxylate (I-307), carboxylate (I-314) to carboxylate (I-322), carboxylate (I-329) to carboxylate (I-334), carboxylate (I-343) to carboxylate (I-345), carboxylate (I-352) to carboxylate (I-360), carboxylate (I-367) to carboxylate (I-372), carboxylate (I-389) to carboxylate (I-396), carboxylate (I-405) to carboxylate (I-412), carboxylate (I-421) to carboxylate (I-428), carboxylate (I-437) to carboxylate (I-444), carboxylate (I-453) to carboxylate (I-460), carboxylate (I-469) to carboxylate (I-476), carboxylate (I-485) to carboxylate (I-492), carboxylate (I-501) to carboxylate (I-508), carboxylate (I-517) to carboxylate (I-524), carboxylate (I-533) to carboxylate (I-540), carboxylate (I-541) to carboxylate (I-543), carboxylate (I-550) to carboxylate (I-558), carboxylate (I-565) to carboxylate (I-570), carboxylate (I-587) to carboxylate (I-597), carboxylate (I-604) to carboxylate (I-612), carboxylate (I-619) to carboxylate (I-624), carboxylate (I-641) to carboxylate (I-651), carboxylate (I-658) to carboxylate (I-666), carboxylate (I-673) to carboxylate (I-678), carboxylate (I-695) to carboxylate (I-705), carboxylate (I-712) to carboxylate (I-720), carboxylate (I-727) to carboxylate (I-732) or carboxylate (I-749) to carboxylate (I-756).

<Method for Producing Carboxylate (I)>

The carboxylate (I) can be produced, for example, by reacting a salt represented by formula (I-a) with a compound represented by formula (I-b) in the presence of a base in a solvent.

wherein all symbols are the same as defined above.

Examples of the base include potassium hydroxide, sodium hydride and the like.

Examples of the solvent include chloroform, monochlorobenzene, acetonitrile, water and the like.

The reaction temperature is usually 15° C. to 100° C., and the reaction time is usually 0.5 to 24 hours.

Examples of the compound represented by formula (I-a) include compounds represented by the following formulas, which are easily available on the market.

Examples of the compound represented by formula (I-b) include compounds represented by the following formulas, which are easily available on the market.

<Resist Composition>

The resist composition of the present invention comprises a carboxylate (I), a resin including a structural unit having an acid-labile group (hereinafter sometimes referred to as “resin (A)”) and an acid generator (hereinafter sometimes referred to as “acid generator (B)”). The “acid-labile group” means a group having a leaving group which is eliminated by contact with an acid, thus forming a hydrophilic group (e.g. a hydroxy group or a carboxy group).

The resist composition of the present invention preferably comprises a solvent (hereinafter sometimes referred to as “solvent (E)”).

The resist composition of the present invention may further comprise a quencher other than the carboxylate (I) (hereinafter sometimes referred to as “quencher (C)”). In this case, particularly, it is preferable to comprise a salt generating an acid having low acidity, such as a weak acid inner salt (D) (hereinafter sometimes referred to as “weak acid inner salt (D)”).

The content of the carboxylate (I) is usually 0.001 to 20% by mass, preferably 0.005 to 15% by mass, and more preferably 0.01 to 10% by mass, based on the amount of the solid component of resist composition.

The carboxylate (I) has a function as a quencher in the resist composition.

<Resin (A)>

The resin (A) includes a structural unit having an acid-labile group (hereinafter sometimes referred to as “structural unit (a1)”). It is preferable that the resin (A) further includes a structural unit other than the structural unit (a1). Examples of the structural unit other than the structural unit (a1) include a structural unit having no acid-labile group (hereinafter sometimes referred to as “structural unit (s)”), a structural unit other than the structural unit (a1) and the structural unit (s) (e.g. a structural unit having a halogen atom mentioned later (hereinafter sometimes referred to as “structural unit (a4)”), a structural unit having a non-leaving hydrocarbon group mentioned later (hereinafter sometimes referred to as “structural unit (a5)”) and other structural units derived from monomers known in the art.

<Structural Unit (a1)>

The structural unit (a1) is derived from a monomer having an acid-labile group (hereinafter sometimes referred to as “monomer (a1)”).

The acid-labile group contained in the resin (A) is preferably a group represented by formula (1) (hereinafter also referred to as group (1)) and/or a group represented by formula (2) (hereinafter also referred to as group (2)):

wherein, in formula (1), R^(a1), R^(a2) and R^(a3) each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group obtained by combining these groups, or R^(a1) and R^(a2) are bonded to each other to form a non-aromatic hydrocarbon ring having 3 to 20 carbon atoms together with carbon atoms to which R^(a1) and R^(a2) are bonded,

ma and na each independently represent 0 or 1, and at least one of ma and na represents 1, and

* represents a bonding site:

wherein, in formula (2), R^(a1′) and R^(a2′) each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R^(a3′) represents a hydrocarbon group having 1 to 20 carbon atoms, or R^(a2′) and R^(a3′) are bonded to each other to form a heterocyclic ring having 3 to 20 carbon atoms together with carbon atoms and X to which R^(a2′) and R^(a3′) are bonded, and —CH₂— included in the hydrocarbon group and the heterocyclic ring may be replaced by —O— or —S—,

X represents an oxygen atom or a sulfur atom,

na′ represents 0 or 1, and

* represents a bonding site.

Examples of the alkyl group in R^(a1), R^(a2) and R^(a3) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like.

Examples of the alkenyl group in R^(a1), R^(a2) and R^(a3) include an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, an isooctenyl group, a nonenyl group and the like.

The alicyclic hydrocarbon group in R^(a1), R^(a1) and R^(a3) may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* represents a bonding site). The number of carbon atoms of the alicyclic hydrocarbon group of R^(a1), R^(a2) and R^(a3) is preferably 3 to 16.

Examples of the aromatic hydrocarbon group in R^(a1), R^(a2) and R^(a3) include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group and a phenanthryl group.

Examples of the combined group include groups obtained by combining the above-mentioned alkyl group and alicyclic hydrocarbon group (e.g., alkylcycloalkyl groups or cycloalkylalkyl groups, such as a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a cyclohexylmethyl group, an adamantylmethyl group, an adamantyldimethyl group and a norbornylethyl group), aralkyl groups such as a benzyl group, aromatic hydrocarbon groups having an alkyl group (a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having an alicyclic hydrocarbon group (a p-cyclohexylphenyl group, a p-adamantylphenyl group, etc.), aryl-cycloalkyl groups such as a phenylcyclohexyl group, and the like.

Preferably, ma is 0 and na is 1.

When R^(a1) and R^(a2) are bonded to each other to form a non-aromatic hydrocarbon ring, examples of —C(R^(a1)) (R^(a2)) (R^(a3)) include the following rings. The non-aromatic hydrocarbon ring preferably has 3 to 12 carbon atoms. * represents a bonding site to —O—.

Examples of the hydrocarbon group in R^(a1′), R^(a2′) and R^(a3′) include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and groups formed by combining these groups.

Examples of the alkyl group and the alicyclic hydrocarbon group include those which are the same as mentioned in R^(a1), R^(a2) and R^(a3).

Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group and a phenanthryl group.

Examples of the combined group include groups obtained by combining the above-mentioned alkyl group and alicyclic hydrocarbon group (e.g., alkylcycloalkyl groups or cycloalkylalkyl groups, such as a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a cyclohexylmethyl group, an adamantylmethyl group, an adamantyldimethyl group and a norbornylethyl group), aralkyl groups such as a benzyl group, aromatic hydrocarbon groups having an alkyl group (a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having an alicyclic hydrocarbon group (a p-cyclohexylphenyl group, a p-adamantylphenyl group, etc.), aryl-cycloalkyl groups such as a phenylcyclohexyl group, and the like.

When R^(a2′) and R^(a3′) are bonded to each other to form a heterocyclic ring together with carbon atoms and X to which R^(a2′) and R^(a3′) are bonded, examples of —C(R^(a1′)) (R^(a2′))—X—R^(a3′) include the following rings. * represents a bonding site.

At least one of R^(a1′) and R^(a2′) is preferably a hydrogen atom.

na′ is preferably 0.

Examples of the group (1) include the following groups.

A group wherein, in formula (1), R^(a1), R^(a2) and R^(a3) are alkyl groups, ma=0 and na=1. The group is preferably a tert-butoxycarbonyl group.

A group wherein, in formula (1), R^(a1) and R^(a2) are bonded to each other to form an adamantyl group together with carbon atoms to which R^(a1) and R^(a2) are bonded, R^(a3) is an alkyl group, ma=0 and na=1.

A group wherein, in formula (1), R^(a1) and R^(a2) are each independently an alkyl group, R^(a3) is an adamantyl group, ma=0 and na=1.

Specific examples of the group (1) include the following groups. * represents a bonding site.

Specific examples of the group (2) include the following groups. * represents a bonding site.

The monomer (a1) is preferably a monomer having an acid-labile group and an ethylenic unsaturated bond, and more preferably a (meth)acrylic monomer having an acid-labile group.

Of the (meth)acrylic monomers having an acid-labile group, those having an alicyclic hydrocarbon group having 5 to 20 carbon atoms are preferably exemplified. When a resin (A) including a structural unit derived from a monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used in a resist composition, it is possible to improve the resolution of a resist pattern.

Examples of the structural unit derived from a (meth)acrylic monomer having a group (1) include a structural unit represented by formula (a1-0) (hereinafter sometimes referred to as structural unit (a1-0)), a structural unit represented by formula (a1-1) (hereinafter sometimes referred to as structural unit (a1-1)) or a structural unit represented by formula (a1-2) (hereinafter sometimes referred to as structural unit (a1-2)). The structural unit is preferably at least one structural unit selected from the group consisting of a structural unit (a1-0), a structural unit (a1-1) and a structural unit (a1-2), and more preferably at least one structural unit selected from the group consisting of a structural unit (a1-1) and a structural unit (a1-2). These structural units may be used alone, or two or more structural units may be used in combination.

In formula (a1-0), formula (a1-1) and formula (a1-2),

L^(a01), L^(a1) and L^(a2) each independently represent —O— or *—O—(CH₂)_(k1)—CO—O—, k1 represents an integer of 1 to 7, and * represents a bonding site to —CO—,

R^(a01), R^(a4) and R^(a5) each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom,

R^(a02), R^(a03) and R^(a04) each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group obtained by combining these groups,

R^(a6) and R^(a7) each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group obtained by combining these groups,

m1 represents an integer of 0 to 14,

n1 represents an integer of 0 to 10, and

n1′ represents an integer of 0 to 3.

R^(a01), R^(a4) and R^(a5) are preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

L^(a01), L^(a1) and L^(a2) are preferably an oxygen atom or *—O—(CH₂)_(k01)—CO—O— (in which k01 is preferably an integer of 1 to 4, and more preferably 1), and more preferably an oxygen atom.

Examples of the alkyl group, the alicyclic hydrocarbon group, the aromatic hydrocarbon group, and the group obtained by combining these groups in R^(a02), R^(a03) and R^(a04) include groups which are the same as mentioned for R^(a1), R^(a2) and R^(a3) of the group (1).

Examples of the alkyl group, the alkenyl group, the alicyclic hydrocarbon group, the aromatic hydrocarbon group, and groups obtained by combining these groups in R^(a6) and R^(a7) include the same groups as mentioned for R^(a1), R^(a2) and R^(a3) of formula (1).

The alkyl group in R^(a02), R^(a03) and R^(a04) is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.

The alkyl group in R^(a6) and R^(a7) is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group or a t-butyl group, and still more preferably an ethyl group, an isopropyl group or a t-butyl group.

The alkenyl group in R^(a6) and R^(a7) is preferably an alkenyl group having 2 to 6 carbon atoms, and more preferably an ethenyl group, a propenyl group, an isopropenyl group or a butenyl group.

The number of carbon atoms of the alicyclic hydrocarbon group as for R^(a02), R^(a03), R^(a04), R^(a6) and R^(a7) is preferably 5 to 12, and more preferably 5 to 10.

The number of carbon atoms of the aromatic hydrocarbon group as for R^(a02), R^(a03), R^(a04), R^(a6) and R^(a7) is preferably 6 to 12, and more preferably 6 to 10.

The total number of carbon atoms of the group obtained by combining the alkyl group with the alicyclic hydrocarbon group is preferably 18 or less.

The total number of carbon atoms of the group obtained by combining the alkyl group with the aromatic hydrocarbon group is preferably 18 or less.

R^(a02) and R^(a03) are preferably an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a phenyl group or a naphthyl group.

R^(a04) is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group.

Preferably, R^(a6) and R^(a7) are each independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group, a phenyl group or a naphthyl group, and still more preferably an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group or a phenyl group.

m1 is preferably an integer of 0 to 3, and more preferably 0 or 1.

n1 is preferably an integer of 0 to 3, and more preferably 0 or 1.

n1′ is preferably 0 or 1.

The structural unit (a1-0) includes, for example, a structural unit represented by any one of formula (a1-0-1) to formula (a1-0-18) and a structural unit in which a methyl group corresponding to R^(a01) in the structural unit (a1-0) is substituted with a hydrogen atom, a halogen atom, a haloalkyl group or other alkyl groups and is preferably a structural unit represented by any one of formula (a1-0-1) to formula (a1-0-10), formula (a1-0-13) and formula (a1-0-14).

The structural unit (a1-1) includes, for example, structural units derived from the monomers mentioned in JP 2010-204646 A. Of these structural units, a structural unit represented by any one of formula (a1-1-1) to formula (a1-1-7) and a structural unit in which a methyl group corresponding to R^(a4) in the structural unit (a1-1) is substituted with a hydrogen atom, a halogen atom, a haloalkyl group or other alkyl groups are preferable, and a structural unit represented by any one of formula (a1-1-1) to formula (a1-1-4) is more preferable.

Examples of the structural unit (a1-2) include a structural unit represented by any one of formula (a1-2-1) to formula (a1-2-14) and a structural unit in which a methyl group corresponding to R^(a)s in the structural unit (a1-2) is substituted with a hydrogen atom, a halogen atom, a haloalkyl group or other alkyl groups, and a structure unit represented by any one of formula (a1-2-2), formula (a1-2-5), formula (a1-2-6) and formula (a1-2-10) to formula (a1-2-14) is preferable.

When the resin (A) includes a structural unit (a1-0), the content thereof is usually 5 to 80 mol %, preferably 5 to 75 mol %, and more preferably 10 to 70 mol %, based on all structural units of the resin (A).

When the resin (A) includes a structural unit (a1-1) and/or a structural unit (a1-2), the total content thereof is usually 10 to 90 mol %, preferably 15 to 85 mol %, more preferably 20 to 80 mol %, still more preferably 20 to 75 mol %, and yet more preferably 20 to 70 mol %, based on all structural units of the resin (A).

In the structural unit (a1), examples of the structural unit having a group (2) include a structural unit represented by formula (a1-4) (hereinafter sometimes referred to as “structural unit (a1-4)”):

wherein, in formula (a1-4),

R^(a32) represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom,

R^(a33) represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group,

A^(a30) represents a single bond or *—X^(a31)-(A^(a32)-X^(a32))_(nc)—, and * represents a bonding site to carbon atoms to which —R^(a32) is bonded,

A^(a32) represents an alkanediyl group having 1 to 6 carbon atoms,

X^(a31) and X^(a32) each independently represent —O—, —CO—O— or —O—CO—,

nc represents 0 or 1,

la represents an integer of 0 to 4, and when la is an integer of 2 or more, a plurality of R^(a33) may be the same or different from each other, and

R^(a34) and R^(a35) each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R^(a36) represents a hydrocarbon group having 1 to 20 carbon atoms, or R^(a35) and R^(a36) are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms together with —C—O— to which R^(a35) and R^(a36) are bonded, and —CH₂— included in the hydrocarbon group and the divalent hydrocarbon group may be replaced by —O— or —S—.

Examples of the halogen atom in R^(a32) and R^(a33) include a fluorine atom, a chlorine atom and a bromine atom.

Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in R^(a22) include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, a hexyl group and a perfluorohexyl group.

R^(a32) is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom or a methyl group.

Examples of the alkyl group in R^(a33) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.

Examples of the alkoxy group in R^(a33) include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group and a hexyloxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and still more preferably a methoxy group.

Examples of the alkoxyalkyl group in R^(a33) include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group and a tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and still more preferably a methoxymethyl group.

Examples of the alkoxyalkoxy group in R^(a33) include a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, a butoxymethoxy group, a sec-butoxymethoxy group and a tert-butoxymethoxy group. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, and more preferably a methoxyethoxy group or an ethoxyethoxy group.

Examples of the alkylcarbonyl group in R^(a33) include an acetyl group, a propionyl group and a butyryl group. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, and more preferably an acetyl group.

Examples of the alkylcarbonyloxy group in R^(a33) include an acetyloxy group, a propionyloxy group and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and more preferably an acetyloxy group.

R^(a33) is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group or an ethoxymethoxy group, and still more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group or an ethoxyethoxy group.

Examples of the *—X^(a31)-(A^(a32)-X^(a32))_(nc)— include *—O—, *—CO—O—, *—O—CO—, +—CO—O-A^(a32)-CO—O—, *—O—CO-A^(a32)-O—, *—O-A^(a32)-CO—O—, *—CO—O-A^(a32)-O—CO— and *—O—CO-A^(a32)-O—CO. Of these, *—CO—O—, *—CO—O-A^(a32)-CO—O— or *—O-A^(a32)-CO—O— is preferable.

Examples of the alkanediyl group in A^(a32) include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group and a 2-methylbutane-1,4-diyl group.

A^(a32) is preferably a methylene group or an ethylene group.

A^(a30) is preferably a single bond, *—CO—O— or *—CO—O-A^(a32)—CO—O—, more preferably a single bond, *—CO—O— or *—CO—O—CH₂—CO—O—, and still more preferably a single bond or *—CO—O—.

la is preferably 0, 1 or 2, more preferably 0 or 1, and still more preferably 0.

Examples of the hydrocarbon group in R^(a34), R^(a35) and R^(a36) include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and groups formed by combining these groups.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like.

The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* represents a bonding site).

Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group and a phenanthryl group.

Examples of the combined group include groups obtained by combining the above-mentioned alkyl group and alicyclic hydrocarbon group (e.g., alkylcycloalkyl groups or cycloalkylalkyl groups, such as a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a cyclohexylmethyl group, an adamantylmethyl group, an adamantyldimethyl group and a norbornylethyl group), aralkyl groups such as a benzyl group, aromatic hydrocarbon groups having an alkyl group (a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having an alicyclic hydrocarbon group (a p-cyclohexylphenyl group, a p-adamantylphenyl group, etc.), aryl-cycloalkyl groups such as a phenylcyclohexyl group and the like. Particularly, examples of R^(a36) include an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these groups.

R^(a34) is preferably a hydrogen atom.

R^(a35) is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a methyl group or an ethyl group.

The hydrocarbon group of R^(a36) is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these groups, and more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an aralkyl group having 7 to 18 carbon atoms. The alkyl group and the alicyclic hydrocarbon group in R^(a36) are preferably unsubstituted. The aromatic hydrocarbon group in R⁴³⁶ is preferably an aromatic ring having an aryloxy group having 6 to 10 carbon atoms.

—OC(R^(a34)) (R^(a35))—O—R^(a36) in the structural unit (a1-4) is eliminated by contacting with an acid (e.g., p-toluenesulfonic acid) to form a hydroxy group.

—OC(R^(a34))(R^(a35))—O—R^(a36) is preferably bonded to the o-position or the p-position of the benzene ring, and more preferably the p-position.

The structural unit (a1-4) includes, for example, structural units derived from the monomers mentioned in JP 2010-204646 A. The structural unit preferably includes structural units represented by formula (a1-4-1) to formula (a1-4-24) and a structural unit in which a hydrogen atom corresponding to R^(a32) in the structural unit (a1-4) is substituted with a halogen atom, a haloalkyl group or an alkyl group, and more preferably structural units represented by formula (a1-4-1) to formula (a1-4-5), formula (a1-4-10), formula (a1-4-13) and formula (a1-4-14).

When the resin (A) includes the structural unit (a1-4), the content is preferably 3 to 80 mol %, more preferably 5 to 75 mol %, still more preferably 7 to 70 mol %, yet more preferably 7 to 65 mol %, and particularly preferably 10 to 60 mol %, based on the total of all structural units of the resin (A).

The structural unit derived from a (meth)acrylic monomer having a group (2) also includes a structural unit represented by formula (a1-5) (hereinafter sometimes referred to as “structural unit (a1-5)”).

In formula (a1-5),

R^(a8) represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom,

Z^(a1) represents a single bond or *—(CH₂)_(h3)—CO-L⁵⁴-, h3 represents an integer of 1 to 4, and * represents a bonding site to L⁵¹,

L⁵¹, L⁵², L⁵³ and L⁵⁴ each independently represent —O— or —S—,

s1 represents an integer of 1 to 3, and

s1′ represents an integer of 0 to 3.

The halogen atom includes a fluorine atom and a chlorine atom and is preferably a fluorine atom. Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a fluoromethyl group and a trifluoromethyl group.

In formula (a1-5), R^(a8) is preferably a hydrogen atom, a methyl group or a trifluoromethyl group,

L⁵¹ is preferably an oxygen atom,

one of L⁵² and L⁵³ is preferably —O— and the other one is preferably —S—,

s1 is preferably 1,

s1′ is preferably an integer of 0 to 2, and

Z^(a1) is preferably a single bond or *—CH₂—CO—.

The structural unit (a1-5) includes, for example, structural units derived from the monomers mentioned in JP 2010-61117 A. Of these structural units, structural units represented by formula (a1-5-1) to formula (a1-5-4) are preferable, and structural units represented by formula (a1-5-1) or formula (a1-5-2) are more preferable.

When the resin (A) includes the structural unit (a1-5), the content is preferably 1 to 50 mol %, more preferably 3 to 45 mol %, still more preferably 5 to 40 mol %, and yet more preferably 5 to 30 mol %, based on all structural units of the resin (A).

The structural unit (a1) also includes the following structural units.

When the resin (A) includes the above-mentioned structural units such as (a1-3-1) to (a1-3-7), the content is preferably 10 to 95 mol %, more preferably 15 to 90 mol %, still more preferably 20 to 85 mol %, yet more preferably 20 to 70 mol %, and particularly preferably 20 to 60 mol %, based on all structural units of the resin (A).

The structural unit (a1) also includes the following structural units.

When the resin (A) includes structural units such as (a1-6-1) to (a1-6-3) mentioned above, the content is preferably 10 to 60 mol %, more preferably 15 to 55 mol %, still more preferably 20 to 50 mol %, yet more preferably 20 to 45 mol %, and particularly preferably 20 to 40 mol %, based on all structural units of the resin (A).

<Structural Unit (s)>

The structural unit (s) is derived from a monomer having no acid-labile group (hereinafter sometimes referred to as “monomer (s)”). It is possible to use, as the monomer from which the structural unit (s) is derived, a monomer having no acid-labile group known in the resist field.

The structural unit (s) preferably has a hydroxy group or a lactone ring. When a resin including a structural unit having a hydroxy group and having no acid-labile group (hereinafter sometimes referred to as “structural unit (a2)”) and/or a structural unit having a lactone ring and having no acid-labile group (hereinafter sometimes referred to as “structural unit (a3)”) is used in the resist composition of the present invention, it is possible to improve the resolution of a resist pattern and the adhesion to a substrate.

<Structural Unit (a2)>

The hydroxy group possessed by the structural unit (a2) may be either an alcoholic hydroxy group or a phenolic hydroxy group.

When a resist pattern is produced from the resist composition of the present invention, in the case of using, as an exposure source, high energy rays such as KrF excimer laser (248 nm), electron beam or extreme ultraviolet light (EUV), a structural unit (a2) having a phenolic hydroxy group is preferably used, and the below-mentioned structural unit (a2-A) is more preferably used, as the structural unit (a2). When using ArF excimer laser (193 nm) or the like, a structural unit (a2) having an alcoholic hydroxy group is preferably used, and the below-mentioned structural unit (a2-1) is more preferably used, as the structural unit (a2). The structural unit (a2) may be included alone, or two or more structural units may be included.

In the structural unit (a2), examples of the structural unit having a phenolic hydroxy group include a structural unit represented by formula (a2-A) (hereinafter sometimes referred to as “structural unit (a2-A)”).

wherein, in formula (a2-A),

R^(a50) represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom,

R^(a51) represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group,

A^(a50) represents a single bond or *—X^(a51)-(A^(a52)-X^(a52))_(nb)—, and * represents a bonding site to carbon atoms to which —R^(a50) is bonded,

A^(a52) represents an alkanediyl group having 1 to 6 carbon atoms,

X^(a51) and X^(a52) each independently represent —O—, —CO—O— or —O—CO—,

nb represents 0 or 1, and

mb represents an integer of 0 to 4, and when mb is an integer of 2 or more, a plurality of R^(a51) may be the same or different from each other.

Examples of the halogen atom in R^(a50) and R^(a51) include a fluorine atom, a chlorine atom and a bromine atom.

Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in R^(a50) include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, a hexyl group and a perfluorohexyl group.

R^(a50) is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom or a methyl group.

Examples of the alkyl group in R^(a51) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.

Examples of the alkoxy group in R^(a51) include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group and a tert-butoxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and still more preferably a methoxy group.

Examples of the alkoxyalkyl group in R^(a51) include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group and a tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and still more preferably a methoxymethyl group.

Examples of the alkoxyalkoxy group in R^(a51) include a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, a butoxymethoxy group, a sec-butoxymethoxy group and a tert-butoxymethoxy group. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, and more preferably a methoxyethoxy group or an ethoxyethoxy group.

Examples of the alkylcarbonyl group in R^(a51) include an acetyl group, a propionyl group and a butyryl group. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, and more preferably an acetyl group.

Examples of the alkylcarbonyloxy group in R^(a51) include an acetyloxy group, a propionyloxy group and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and more preferably an acetyloxy group.

R^(a51) is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group or an ethoxymethoxy group, and still more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group or an ethoxyethoxy group.

Examples of *—X^(a51)-(A^(a52)-X^(a52))_(nb)— include *—O—, *—CO—O—, *—O—CO—, *—CO—O-A^(a52)-CO—O—, *—O—CO-A^(a52)-O—, *—O-A^(a52)-CO—O—, *—CO—O-A^(a52)-O—CO— and *—O—CO-A^(a52)-O—CO—. Of these, *—CO—O—, *—CO—O-A^(a52)-CO—O— or *—O-A^(a52)-CO—O— is preferable.

Examples of the alkanediyl group in A^(a52) include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group and a 2-methylbutane-1,4-diyl group.

A^(a52) is preferably a methylene group or an ethylene group.

A^(a50) is preferably a single bond, *—CO—O— or *—CO—O-A^(a52)-CO—O—, more preferably a single bond, *—CO—O— or *—CO—O—CH₂—CO—O—, and still more preferably a single bond or *—CO—O—.

mb is preferably 0, 1 or 2, more preferably 0 or 1, and still more preferably 0.

The hydroxy group is preferably bonded to the o-position or the p-position of a benzene ring, and more preferably the p-position.

Examples of the structural unit (a2-A) include structural units derived from the monomers mentioned in JP 2010-204634 A and JP 2012-12577 A.

Examples of the structural unit (a2-A) include structural units represented by formula (a2-2-1) to formula (a2-2-24), and a structural unit in which a methyl group corresponding to R^(a50) in the structural unit (a2-A) is substituted with a hydrogen atom, a halogen atom, a haloalkyl group or other alkyl groups in structural units represented by formula (a2-2-1) to formula (a2-2-24). The structural unit (a2-A) is preferably a structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2-6), a structural unit represented by formula (a2-2-8), structural units represented by formula (a2-2-12) to formula (a2-2-14), and structural units in which a methyl group corresponding to R^(a50) in the structural unit (a2-A) is substituted with a hydrogen atom in a structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2-6), a structural unit represented by formula (a2-2-8) and structural units represented by formula (a2-2-12) to formula (a2-2-14), more preferably a structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2-8), structural units represented by formula (a2-2-12) to formula (a2-2-14), and structural units in which a methyl group corresponding to R^(a50) in the structural unit (a2-A) is substituted with a hydrogen atom in a structural unit represented by formula (a2-2-3) or a structural unit represented by formula (a2-2-8) and structural units represented by formula (a2-2-12) to formula (a2-2-14), and still more preferably a structural unit represented by formula (a2-2-8) and a structural unit in which a methyl group corresponding to R^(a50) in the structural unit (a2-A) is substituted with a hydrogen atom in a structural unit represented by formula (a2-2-8).

When the structural unit (a2-A) is included in the resin (A), the content of the structural unit (a2-A) is preferably 5 to 80 mol %, more preferably 10 to 70 mol %, still more preferably 15 to 65 mol %, and yet more preferably 20 to 65 mol %, based on all structural units.

The structural unit (a2-A) can be included in a resin (A) by polymerizing, for example, with a structural unit (a1-4) and treating with an acid such as p-toluenesulfonic acid. The structural unit (a2-A) can also be included in the resin (A) by polymerizing with acetoxystyrene and treating with an alkali such as tetramethylammonium hydroxide.

Examples of the structural unit having an alcoholic hydroxy group in the structural unit (a2) include a structural unit represented by formula (a2-1) (hereinafter sometimes referred to as “structural unit (a2-1)”).

In formula (a2-1),

L^(a3) represents —O— or *—O—(CH₂)_(k2)—CO—O—,

k2 represents an integer of 1 to 7, and * represents a bonding site to —CO—,

R^(a14) represents a hydrogen atom or a methyl group,

R^(a15) and R^(a16) each independently represent a hydrogen atom, a methyl group or a hydroxy group, and

o1 represents an integer of 0 to 10.

In formula (a2-1), L^(a3) is preferably —O— or —O—(CH₂)^(f1)—CO—O— (f1 represents an integer of 1 to 4), and more preferably —O—,

R^(a14) is preferably a methyl group,

R^(a15) is preferably a hydrogen atom,

R^(a16) is preferably a hydrogen atom or a hydroxy group, and

o1 is preferably an integer of 0 to 3, and more preferably 0 or 1.

The structural unit (a2-1) includes, for example, structural units derived from the monomers mentioned in JP 2010-204646 A. A structural unit represented by any one of formula (a2-1-1) to formula (a2-1-6) is preferable, a structural unit represented by any one of formula (a2-1-1) to formula (a2-1-4) is more preferable, and a structural unit represented by formula (a2-1-1) or formula (a2-1-3) is still more preferable.

When the resin (A) includes the structural unit (a2-1), the content is usually 1 to 45 mol %, preferably 1 to 40 mol %, more preferably 1 to 35 mol %, still more preferably 1 to 20 mol %, and yet more preferably 1 to 10 mol %, based on all structural units of the resin (A).

<Structural Unit (a3)>

The lactone ring possessed by the structural unit (a3) may be a monocyclic ring such as a β-propiolactone ring, a γ-butyrolactone ring or a δ-valerolactone ring, or a condensed ring of a monocyclic lactone ring and the other ring. Preferably, a γ-butyrolactone ring, an adamantanelactone ring or a bridged ring including a γ-butyrolactone ring structure (e.g. a structural unit represented by the following formula (a3-2)) is exemplified.

The structural unit (a3) is preferably a structural unit represented by formula (a3-1), formula (a3-2), formula (a3-3) or formula (a3-4). These structural units may be included alone, or two or more structural units may be included:

wherein, in formula (a3-1), formula (a3-2), formula (a3-3) and formula (a3-4),

L^(a4), L^(a5) and L^(a6) each independently represent —O— or a group represented by *—O—(CH₂)_(k3)—CO—O— (k3 represents an integer of 1 to 7),

L^(a7) represents —O—, *—O-L^(a8)-O—, *—O-L^(a8)-CO—O—, *—O-L^(a8)-CO—O-L^(a9)-CO—O— or *—O-L^(a8)-O—CO-L^(a9)-O—,

L^(a8) and L^(a9) each independently represent an alkanediyl group having 1 to 6 carbon atoms,

* represents a bonding site to a carbonyl group,

R^(a18), R^(a19) and R^(a20) each independently represent a hydrogen atom or a methyl group,

R^(a24) represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom,

X^(a3) represents —CH₂— or an oxygen atom,

R^(a21) represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms,

R^(a22), R^(a23) and R^(a25) each independently represent a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms,

p1 represents an integer of 0 to 5,

q1 represents an integer of 0 to 3,

r1 represents an integer of 0 to 3,

w1 represents an integer of 0 to 8, and

when p1, q1, r1 and/or w1 is/are 2 or more, a plurality of R^(a21), R^(a22), R^(a23) and/or R^(a25) may be the same or different from each other.

Examples of the aliphatic hydrocarbon group in R^(a21), R^(a22), R^(a23) and R^(a25) include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group and a tert-butyl group.

Examples of the halogen atom in R^(a24) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkyl group in R^(a24) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group, and the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.

Examples of the alkyl group having a halogen atom in R^(a24) include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group and the like.

Examples of the alkanediyl group in L^(a8) and L^(a9) include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group and a 2-methylbutane-1,4-diyl group.

In formula (a3-1) to formula (a3-3), preferably, L^(a4) to L⁴⁶ are each independently —O— or a group in which k3 is an integer of 1 to 4 in *—O—(CH₂)_(k3)—CO—O—, more preferably —O— and *—O—CH₂—CO—O—, and still more preferably an oxygen atom,

R^(a18) to R^(a21) are preferably a methyl group,

preferably, R^(a22) and R^(a23) are each independently a carboxy group, a cyano group or a methyl group, and preferably, p1, q1 and r1 are each independently an integer of 0 to 2, and more preferably 0 or 1.

In formula (a3-4), R^(a24) is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom or a methyl group,

R^(a25) is preferably a carboxy group, a cyano group or a methyl group,

L^(a7) is preferably —O— or *—O-L^(a3)-CO—O—, and more preferably —O—, —O—CH₂—CO—O— or —O—C₂H₄—CO—O—, and

w1 is preferably an integer of 0 to 2, and more preferably 0 or 1.

Particularly, formula (a3-4) is preferably formula (a3-4)′:

wherein R^(a24) and L^(a7) are the same as defined above.

Examples of the structural unit (a3) include structural units derived from the monomers mentioned in JP 2010-204646 A, the monomers mentioned in JP 2000-122294 A and the monomers mentioned in JP 2012-41274 A. The structural unit (a3) is preferably a structural unit represented by any one of formula (a3-1-1), formula (a3-1-2), formula (a3-2-1), formula (a3-2-2), formula (a3-3-1), formula (a3-3-2) and formula (a3-4-1) to formula (a3-4-12), and structural units in which methyl groups corresponding to R^(a18), R^(a19), R^(a20) and R^(a24) in formula (a3-1) to formula (a3-4) are substituted with hydrogen atoms in the above structural units.

When the resin (A) includes the structural unit (a3), the total content is usually 5 to 70 mol %, preferably 10 to 65 mol %, and more preferably 10 to 60 mol %, based on all structural units of the resin (A).

Each content of the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) or the structural unit (a3-4) is preferably 5 to 60 mol %, more preferably 5 to 50 mol %, and still more preferably 10 to 50 mol %, based on all structural units of the resin (A).

<Structural Unit (a4)>

Examples of the structural unit (a4) include the following structural unit:

wherein, in formula (a4),

-   -   R⁴¹ represents a hydrogen atom or a methyl group, and     -   R⁴² represents a saturated hydrocarbon group having 1 to 24         carbon atoms which has a halogen atom, and —CH₂— included in the         saturated hydrocarbon group may be replaced by —O— or —CO—.

Examples of the saturated hydrocarbon group represented by R⁴² include a chain saturated hydrocarbon group and a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and groups formed by combining these groups.

Examples of the chain saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group.

Examples of the monocyclic or polycyclic alicyclic saturated hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; and polycyclic alicyclic saturated hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* represents a bonding site).

Examples of the group formed by combination include groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic saturated hydrocarbon groups, and include an -alkanediyl group-alicyclic saturated hydrocarbon group, an -alicyclic saturated hydrocarbon group-alkyl group, an -alkanediyl group-alicyclic saturated hydrocarbon group-alkyl group and the like.

Examples of the structural unit (a4) include a structural unit represented by formula (a4-0), a structural unit represented by formula (a4-1) and a structural unit represented by formula (a4-4):

wherein, in formula (a4-0),

R⁵⁴ represents a hydrogen atom or a methyl group,

L^(4a) represents a single bond or an alkanediyl group having 1 to 4 carbon atoms,

L^(3a) represents a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluorocycloalkanediyl group having 3 to 12 carbon atoms, and

-   -   R⁶⁴ represents a hydrogen atom or a fluorine atom.

Examples of the alkanediyl group in L^(4a) include linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group and a butane-1,4-diyl group; and branched alkanediyl groups such as an ethane-1,1-diyl group, a propane-1,2-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group and a 2-methylpropane-1,2-diyl group.

Examples of the perfluoroalkanediyl group in L^(3a) include a difluoromethylene group, a perfluoroethylene group, a perfluoroethylfluoromethylene group, a perfluoropropane-1,3-diyl group, a perfluoropropane-1,2-diyl group, a perfluoropropane-2,2-diyl group, a perfluorobutane-1,4-diyl group, a perfluorobutane-2,2-diyl group, a perfluorobutane-1,2-diyl group, a perfluoropentane-1,5-diyl group, a perfluoropentane-2,2-diyl group, a perfluoropentane-3,3-diyl group, a perfluorohexane-1,6-diyl group, a perfluorohexane-2,2-diyl group, a perfluorohexane-3,3-diyl group, a perfluoroheptane-1,7-diyl group, a perfluoroheptane-2,2-diyl group, a perfluoroheptane-3,4-diyl group, a perfluoroheptane-4,4-diyl group, a perfluorooctane-1,8-diyl group, a perfluorooctane-2,2-diyl group, a perfluorooctane-3,3-diyl group, a perfluorooctane-4,4-diyl group and the like.

Examples of the perfluorocycloalkanediyl group in L^(3a) include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group, a perfluoroadamantanediyl group and the like.

L^(4a) is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond or a methylene group.

L^(3a) is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, and more preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms.

Examples of the structural unit (a4-0) include the following structural units, and structural units in which a methyl group corresponding to R⁵⁴ in the structural unit (a4-0) in the following structural units is substituted with a hydrogen atom:

wherein, in formula (a4-1),

R^(a41) represents a hydrogen atom or a methyl group,

R^(a42) represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and —CH₂— included in the saturated hydrocarbon group may be replaced by —O— or —CO—,

A^(a41) represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or a group represented by formula (a-g1), in which at least one of A^(a41) and R^(a42) has, as a substituent, a halogen atom (preferably a fluorine atom):

[in which, in formula (a-g1),

s represents 0 or 1,

A^(a42) and A^(a44) each independently represent a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent,

A^(a43) represents a single bond or a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent,

X^(a41) and X^(a42) each independently represent —O—, —CO—, —CO—O— or —O—CO—, in which the total number of carbon atoms of A^(a42), A^(a43), A^(a44), X^(a41) and X^(a42) is 7 or less], and

* represents a bonding site and * at the right side represents a bonding site to —O—CO—R^(a42).

Examples of the saturated hydrocarbon group in R^(a42) include a chain saturated hydrocarbon group and a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and groups formed by combining these groups.

Examples of the chain saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group.

Examples of the monocyclic or polycyclic alicyclic saturated hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; and polycyclic alicyclic saturated hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* represents a bonding site).

Examples of the group formed by combination include groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic saturated hydrocarbon groups, and include an -alkanediyl group-alicyclic saturated hydrocarbon group, an -alicyclic saturated hydrocarbon group-alkyl group, an -alkanediyl group-alicyclic saturated hydrocarbon group-alkyl group and the like.

Examples of the substituent which is possessed by R^(a42) include at least one selected from the group consisting of a halogen atom and a group represented by formula (a-g3). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable:

*—X^(a43)-A^(a45)  (a-g3)

wherein, in formula (a-g3),

X^(a43) represents an oxygen atom, a carbonyl group, *—O—CO— or *—CO—O—,

A^(a45) represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom, and

* represents a bonding site to R^(a42).

In R^(a42)—X^(a43)-A^(a45), when R^(a42) has no halogen atom, A^(a45) represents a saturated hydrocarbon group having 1 to 17 carbon atoms having at least one halogen atom.

Examples of the saturated hydrocarbon group in A^(a45) include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group;

monocyclic alicyclic hydrocarbon groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* represents a bonding site).

Examples of the group formed by combination include a group obtained by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic hydrocarbon groups, and include an -alkanediyl group-alicyclic hydrocarbon group, an -alicyclic hydrocarbon group-alkyl group, an -alkanediyl group-alicyclic hydrocarbon group-alkyl group and the like.

R^(a42) is preferably a saturated hydrocarbon group which may have a halogen atom, and more preferably an alkyl group having a halogen atom and/or a saturated hydrocarbon group having a group represented by formula (a-g3).

When R^(a42) is a saturated hydrocarbon group having a halogen atom, a saturated hydrocarbon group having a fluorine atom is preferable, a perfluoroalkyl group or a perfluorocycloalkyl group is more preferable, a perfluoroalkyl group having 1 to 6 carbon atoms is still more preferable, and a perfluoroalkyl group having 1 to 3 carbon atoms is particularly preferable. Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group and a perfluorooctyl group. Examples of the perfluorocycloalkyl group include a perfluorocyclohexyl group and the like.

When R^(a42) is a saturated hydrocarbon group having a group represented by formula (a-g3), the total number of carbon atoms of R^(a42) is preferably 15 or less, and more preferably 12 or less, including the number of carbon atoms included in the group represented by formula (a-g3). When having the group represented by formula (a-g3) as the substituent, the number thereof is preferably 1.

When R^(a42) is a saturated hydrocarbon group having the group represented by formula (a-g3), R^(a42) is still more preferably a group represented by formula (a-g2):

*-A^(a46)-X^(a44)-A^(a47)  (a-g2)

wherein, in formula (a-g2),

A^(a46) represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom,

X^(a44) represents **—O—CO— or **—CO—O— (** represents a bonding site to A^(a46)),

A^(a47) represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom,

the total number of carbon atoms of A^(a46), A^(a47) and X^(a44) is 18 or less, and at least one of A^(a46) and A^(a47) has at least one halogen atom, and

* represents a bonding site to a carbonyl group.

The number of carbon atoms of the saturated hydrocarbon group as for A^(a46) is preferably 1 to 6, and more preferably 1 to 3.

The number of carbon atoms of the saturated hydrocarbon group as for A^(a47) is preferably 4 to 15, and more preferably 5 to 12, and A^(a47) is still more preferably a cyclohexyl group or an adamantyl group.

Preferred structures of the group represented by formula (a-g2) are the following structures (* represents a bonding site to a carbonyl group).

Examples of the alkanediyl group in A^(a41) include linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group and a hexane-1,6-diyl group; and branched alkanediyl groups such as a propane-1,2-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a 1-methylbutane-1,4-diyl group and a 2-methylbutane-1,4-diyl group.

Examples of the substituent in the alkanediyl group represented by A^(a41) include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.

A^(a41) is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and still more preferably an ethylene group.

Examples of the divalent saturated hydrocarbon group represented by A^(a42), A^(a43) and A^(a44) in the group represented by formula (a-g1) include a linear or branched alkanediyl group and a monocyclic divalent alicyclic saturated hydrocarbon group, and a divalent saturated hydrocarbon group formed by combining an alkanediyl group and a divalent alicyclic saturated hydrocarbon group. Specific examples thereof include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a 1-methylpropane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group and the like.

Examples of the substituent of the divalent saturated hydrocarbon group represented by A^(a42), A^(a43) and A^(a44) include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.

s is preferably 0.

In the group represented by formula (a-g1), examples of the group in which X^(a42) is —O—, —CO—, —CO—O— or —O—CO— include the following groups. In the following exemplification, * and ** each represent a bonding site, and ** represents a bonding site to —O—CO—R^(a42),

Examples of the structural unit represented by formula (a4-1) include the following structural units, and structural units in which a methyl group corresponding to R^(a41) in the structural unit represented by formula (a4-1) in the following structural units is substituted with a hydrogen atom.

Examples of the structural unit represented by formula (a4-1) include a structural unit represented by formula (a4-2) and a structural unit represented by formula (a4-3):

wherein, in formula (a4-2),

R^(f5) represents a hydrogen atom or a methyl group,

L⁴⁴ represents an alkanediyl group having 1 to 6 carbon atoms, and —CH₂— included in the alkanediyl group may be replaced by —O— or —CO—,

R^(f6) represents a saturated hydrocarbon group having 1 to 20 carbon atoms having a fluorine atom, and

the upper limit of the total number of carbon atoms of L⁴⁴ and R^(f6) is 21.

Examples of the alkanediyl group having 1 to 6 carbon atoms of L⁴⁴ include those which are the same as mentioned as for A^(a41).

Examples of the saturated hydrocarbon group of R^(f6) include the same groups as mentioned for R⁴².

The alkanediyl group in L⁴⁴ is preferably an alkanediyl group having 2 to 4 carbon atoms, and more preferably an ethylene group.

The structural unit represented by formula (a4-2) includes, for example, structural units represented by formula (a4-1-1) to formula (a4-1-11). A structural unit in which a methyl group corresponding to R^(f5) in the structural unit (a4-2) is substituted with a hydrogen atom is also exemplified as the structural unit represented by formula (a4-2):

wherein, in formula (a4-3),

R^(f7) represents a hydrogen atom or a methyl group,

L⁵ represents an alkanediyl group having 1 to 6 carbon atoms,

A^(f13) represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom, X^(f12) represents *—O—CO— or *—CO—O— (* represents a bonding site to A^(f13)),

A^(f14) represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a fluorine atom, and at least one of A^(f13) and A^(f14) has a fluorine atom, and the upper limit of the total number of carbon atoms of L⁵, A^(f13) and A^(f14) is 20.

Examples of the alkanediyl group in L⁵ include those which are the same as mentioned in the alkanediyl group as for A^(a41).

The divalent saturated hydrocarbon group which may have a fluorine atom in A^(f13) is preferably a divalent chain saturated hydrocarbon group which may have a fluorine atom and a divalent alicyclic saturated hydrocarbon group which may have a fluorine atom, and more preferably a perfluoroalkanediyl group.

Examples of the divalent chain saturated hydrocarbon group which may have a fluorine atom include alkanediyl groups such as a methylene group, an ethylene group, a propanediyl group, a butanediyl group and a pentanediyl group; and perfluoroalkanediyl groups such as a difluoromethylene group, a perfluoroethylene group, a perfluoropropanediyl group, a perfluorobutanediyl group and a perfluoropentanediyl group.

The divalent alicyclic saturated hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the monocyclic group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic group include an adamantanediyl group, a norbornanediyl group, a perfluoroadamantanediyl group and the like.

Examples of the saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom for A^(f14) include the same groups as mentioned for R^(a42). Of these groups, preferable are fluorinated alkyl groups such as a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, a hexyl group, a perfluorohexyl group, a heptyl group, a perfluoroheptyl group, an octyl group and a perfluorooctyl group; a cyclopropylmethyl group, a cyclopropyl group, a cyclobutylmethyl group, a cyclopentyl group, a cyclohexyl group, a perfluorocyclohexyl group, an adamantyl group, an adamantylmethyl group, an adamantyldimethyl group, a norbornyl group, a norbornylmethyl group, a perfluoroadamantyl group, a perfluoroadamantylmethyl group and the like.

In formula (a4-3), L⁵ is preferably an ethylene group.

The divalent saturated hydrocarbon group of A^(f13) is preferably a group including a divalent chain saturated hydrocarbon group having 1 to 6 carbon atoms and a divalent alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably a divalent chain saturated hydrocarbon group having 2 to 3 carbon atoms.

The saturated hydrocarbon group of A^(f14) is preferably a group including a chain saturated hydrocarbon group having 3 to 12 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably a group including a chain saturated hydrocarbon group having 3 to 10 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms. Of these groups, A^(f14) is preferably a group including an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably a cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group.

The structural unit represented by formula (a4-3) includes, for example, structural units represented by formula (a4-1′-1) to formula (a4-1′-11). A structural unit in which a methyl group corresponding to R^(f7) in the structural unit (a4-3) is substituted with a hydrogen atom is also exemplified as the structural unit represented by formula (a4-3).

It is also possible to exemplify, as the structural unit (a4), a structural unit represented by formula (a4-4):

wherein, in formula (a4-4),

R^(f21) represents a hydrogen atom or a methyl group,

A^(f21) represents —(CH₂)_(j1)—, —(CH₂)_(j2)—O—(CH₂)_(j3)— or —(CH₂)_(j4)—CO—O—(CH₂)_(j5)—,

j1 to j5 each independently represent an integer of 1 to 6, and

R^(f22) represents a saturated hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom.

Examples of the saturated hydrocarbon group of R^(f22) include those which are the same as the saturated hydrocarbon group represented by R^(a42). R^(f22) is preferably an alkyl group having 1 to 10 carbon atoms which has a fluorine atom or an alicyclic saturated hydrocarbon group having 1 to 10 carbon atoms which has a fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms which has a fluorine atom, and still more preferably an alkyl group having 1 to 6 carbon atoms which has a fluorine atom.

In formula (a4-4), A^(f21) is preferably —(CH₂)_(j1)—, more preferably an ethylene group or a methylene group, and still more preferably a methylene group.

The structural unit represented by formula (a4-4) includes, for example, the following structural units and structural units in which a methyl group corresponding to R^(f21) in the structural unit (a4-4) is substituted with a hydrogen atom in structural units represented by the following formulas.

When the resin (A) includes the structural unit (a4), the content is preferably 1 to 20 mol %, more preferably 2 to 15 mol %, and still more preferably 3 to 10 mol %, based on all structural units of the resin (A).

<Structural Unit (a5)>

Examples of a non-leaving hydrocarbon group possessed by the structural unit (a5) include groups having a linear, branched or cyclic hydrocarbon group. Of these, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group.

The structural unit (a5) includes, for example, a structural unit represented by formula (a5-1):

wherein, in formula (a5-1),

-   -   R⁵¹ represents a hydrogen atom or a methyl group,     -   R⁵² represents an alicyclic hydrocarbon group having 3 to 18         carbon atoms, and a hydrogen atom included in the alicyclic         hydrocarbon group may be substituted with an aliphatic         hydrocarbon group having 1 to 8 carbon atoms, and     -   L⁵⁵ represents a single bond or a divalent saturated hydrocarbon         group having 1 to 18 carbon atoms, and —CH₂— included in the         saturated hydrocarbon group may be replaced by —O— or —CO—.

The alicyclic hydrocarbon group in R⁵² may be either monocyclic or polycyclic. The monocyclic alicyclic hydrocarbon group includes, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. The polycyclic alicyclic hydrocarbon group includes, for example, an adamantyl group and a norbornyl group.

The aliphatic hydrocarbon group having 1 to 8 carbon atoms includes, for example, alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group and a 2-ethylhexyl group.

Examples of the alicyclic hydrocarbon group having a substituent includes a 3-methyladamantyl group and the like.

R⁵² is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably an adamantyl group, a norbornyl group or a cyclohexyl group.

Examples of the divalent saturated hydrocarbon group in L⁵⁵ include a divalent chain saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, and a divalent chain saturated hydrocarbon group is preferable.

The divalent chain saturated hydrocarbon group includes, for example, alkanediyl groups such as a methylene group, an ethylene group, a propanediyl group, a butanediyl group and a pentanediyl group.

The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include cycloalkanediyl groups such as a cyclopentanediyl group and a cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantanediyl group and a norbornanediyl group.

The group in which —CH₂— included in the divalent saturated hydrocarbon group represented by L⁵⁵ is replaced by —O— or —CO— includes, for example, groups represented by formula (L1-1) to formula (L1-4). In the following formulas, * and ** each represent a bonding site, and * represents a bonding site to an oxygen atom.

In formula (L1-1),

X^(x1) represents *—O—CO— or *—CO—O— (* represents a bonding site to L^(x1)),

L^(x1) represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms,

L^(x2) represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms, and the total number of carbon atoms of L^(x1) and L^(x2) is 16 or less.

In formula (L1-2),

L^(x3) represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms,

L^(x4) represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms, and

the total number of carbon atoms of L^(x3) and L^(x4) is 17 or less.

In formula (L1-3),

L^(x5) represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms,

L^(x6) and L^(x7) each independently represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms, and

the total number of carbon atoms of L^(x5), L^(x6) and L^(x7) is 15 or less.

In formula (L1-4),

L^(x8) and L^(x9) represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms,

W^(x1) represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms, and

the total number of carbon atoms of L^(x8), L^(x9) and W^(x1) is 15 or less.

L^(x1) is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.

L^(x2) is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a single bond.

L^(x3) is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.

L^(x4) is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.

L^(x5) is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.

L^(x6) is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.

L^(x7) is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.

L^(x8) is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a single bond or a methylene group.

L^(x9) is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a single bond or a methylene group.

W^(x1) is preferably a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, and more preferably a cyclohexanediyl group or an adamantanediyl group.

The group represented by formula (L1-1) includes, for example, the following divalent groups.

The group represented by formula (L1-2) includes, for example, the following divalent groups.

The group represented by formula (L1-3) includes, for example, the following divalent groups.

The group represented by formula (L1-4) includes, for example, the following divalent groups.

L⁵⁵ is preferably a single bond or a group represented by formula (L1-1).

Examples of the structural unit (a5-1) include the following structural units and structural units in which a methyl group corresponding to R⁵¹ in the structural unit (a5-1) in the following structural units is substituted with a hydrogen atom.

When the resin (A) includes the structural unit (a5), the content is preferably 1 to 30 mol %, more preferably 2 to 20 mol %, and still more preferably 3 to 15 mol %, based on all structural units of the resin (A).

<Structural Unit (a6)>

The structural unit (a6) is a structural unit having an —SO₂— group, and it is preferable to have an —SO₂— group in a side chain.

The structural unit having an —SO₂— group may have a linear structure having an —SO₂— group, a branched structure having an —SO₂— group, or a cyclic structure (monocyclic and polycyclic structure) having an —SO₂— group. The structural unit is preferably a structural unit which has a cyclic structure having an —SO₂— group, and more preferably a structural unit which has a cyclic structure (sultone ring) having —SO₂—O—.

Examples of the sultone ring include rings represented by the following formula (T¹-1), formula (T¹-2), formula (T¹-3) and formula (T¹-4). The bonding site can be any position. The sultone ring may be monocyclic, and is preferably polycyclic. The polycyclic sultone ring means a bridged ring which has —SO₂—O— as an atomic group constituting the ring, and examples thereof include rings represented by formula (T¹-1) and formula (T¹-2). The sultone ring may have, as the atomic group constituting the ring, a heteroatom, in addition to —SO₂—O—, like the ring represented by formula (T¹-2). Examples of the heteroatom include an oxygen atom, a sulfur atom or a nitrogen atom, and an oxygen atom is preferable.

The sultone ring may have a substituent, and examples of the substituent include an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms and an alkylcarbonyl group having 2 to 4 carbon atoms.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group and a decyl group, and the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group.

Examples of the alkyl group having a halogen atom include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group and a triiodomethyl group, and a trifluoromethyl group is preferable.

Examples of the alkyl group having a hydroxy group include hydroxyalkyl groups such as a hydroxymethyl group and a 2-hydroxyethyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and a dodecyloxy group.

Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, a p-tert-butylphenyl group, a p-adamantylphenyl group, a tolyl group, a xylyl group, a cumyl group, a mesityl group, a biphenyl group, a phenanthryl group, a 2,6-diethylphenyl group and a 2-methyl-6-ethylphenyl group.

Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and a naphthylethyl group.

Examples of the alkoxycarbonyl group include groups in which an alkoxy group is bonded with a carbonyl group, such as a methoxycarbonyl group or an ethoxycarbonyl group, and preferably include an alkoxycarbonyl group having 6 or less carbon atoms and more preferably include a methoxycarbonyl group.

Examples of the alkylcarbonyl group include an acetyl group, a propionyl group and a butyryl group.

From the viewpoint that it is easy to produce a monomer from which the structural unit (a6) is derived, a sultone ring having no substituent is preferable.

The sultone ring is preferably a ring represented by the following formula (T1′):

wherein, in formula (T1′),

X¹¹ represents an oxygen atom, a sulfur atom or a methylene group,

R⁴¹ represents an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an alkylcarbonyl group having 2 to 4 carbon atoms,

ma represents an integer of 0 to 9, and when ma is 2 or more, a plurality of R⁴¹ may be the same or different, and the bonding site may be at any position.

X¹¹ is preferably an oxygen atom or a methylene group, and more preferably a methylene group.

Examples of R⁴¹ include those which are the same as the substituent of the sultone ring, and an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group is preferable.

The sultone ring is more preferably a ring represented by formula (T1):

wherein, in formula (T1),

R⁸ represents an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an alkylcarbonyl group having 2 to 4 carbon atoms,

m represents an integer of 0 to 9, and when m is 2 or more, a plurality of R³ may be the same or different, and

the bonding site may be at any position.

Examples of R⁸ include those which are the same as for R⁴¹.

ma in formula (T1′) and m in formula (T1) are preferably 0 or 1, and more preferably 0.

Examples of the ring represented by formula (T1′) and the ring represented by formula (T1) include the following rings. The bonding site may be at any position.

It is preferable that the structural unit having a sultone ring has the following groups. * in the following groups represents a bonding site.

It is preferable that the structural unit having an SO₂— group further has a group derived from a polymerizable group. Examples of the polymerizable group include a vinyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, an acryloylthio group, a methacryloylthio group and the like.

Particularly, the monomer from which the structural unit (a6) is derived is preferably a monomer having an ethylenically unsaturated bond, and more preferably a (meth)acrylic monomer.

The structural unit (a6) is preferably a structural unit represented by formula (Ix):

wherein, in formula (Ix), R^(x) represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom,

A^(xx) represents an oxygen atom, —N(R^(c))— or a sulfur atom,

A^(x) represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and —CH₂— included in the saturated hydrocarbon group may be replaced by —O—, —CO— or —N(R^(d))—,

X¹¹ represents an oxygen atom, a sulfur atom or a methylene group,

R⁴¹ represents an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an alkylcarbonyl group having 2 to 4 carbon atoms,

ma represents an integer of 0 to 9, and when ma is 2 or more, a plurality of R⁴¹ may be the same or different, and

R^(c) and R^(d) each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Examples of the halogen atom as for R^(x) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkyl group as for R^(x) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and an n-hexyl group, and an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.

Examples of the alkyl group having a halogen atom as for R^(x) include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group and a triiodomethyl group.

R^(x) is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom or a methyl group.

Examples of the divalent saturated hydrocarbon group as for A^(x) include a linear alkanediyl group, a branched alkanediyl group and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and the divalent saturated hydrocarbon group may be those obtained by combining two or more of these groups.

Specific examples thereof include linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1,14-diyl group, a pentadecane-1,15-diyl group, a hexadecane-1,16-diyl group, a heptadecane-1,17-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group and a propane-2,2-diyl group;

branched alkanediyl groups such as a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group and a 2-methylbutane-1,4-diyl group;

monocyclic divalent alicyclic saturated hydrocarbon groups which are cycloalkanediyl groups such as a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group and a cyclooctane-1,5-diyl group; and

polycyclic divalent alicyclic saturated hydrocarbon groups such as a norbornane-1,4-diyl group, a norbornane-2,5-diyl group, an adamantane-1,5-diyl group and an adamantane-2,6-diyl group.

Examples of R⁴¹, X¹¹ and ma include those which are the same as in formula (T1′).

Examples of the sultone ring include those mentioned above, and of these, preferred are the above-mentioned rings in which the bonding site is specified.

Examples of the structural unit (a6) include the following structural units.

Of these, structural units represented by formula (a6-1), formula (a6-2), formula (a6-6), formula (a6-7), formula (a6-8) and formula (a6-12) are preferable, and structural units represented by formula (a6-1), formula (a6-2), formula (a6-7) and (a6-8) are more preferable.

When the resin (A) includes the structural unit (a6), the content is preferably 1 to 50 mol %, more preferably 2 to 40 mol %, and still more preferably 3 to 30 mol %, based on all structural units of the resin (A).

<Structural Unit (II)>

The resin (A) may further include a structural unit which is decomposed upon exposure to radiation to generate an acid (hereinafter sometimes referred to as “structural unit (II)”). Specific examples of the structural unit (II) include the structural units mentioned in JP 2016-79235 A, and a structural unit having a sulfonate group or a carboxylate group and an organic cation in a side chain or a structural unit having a sulfonio group and an organic anion in a side chain are preferable.

The structural unit having a sulfonate group or a carboxylate group and an organic cation in a side chain is preferably a structural unit represented by formula (II-2-A′):

wherein, in formula (II-2-A′),

X^(III3) represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, —CH₂— included in the saturated hydrocarbon group may be replaced by —O—, —S— or —CO—, and a hydrogen atom included in the saturated hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, or a hydroxy group,

A^(x1) represents an alkanediyl group having 1 to 8 carbon atoms, and a hydrogen atom included in the alkanediyl group may be substituted with a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms,

RA⁻ represents a sulfonate group or a carboxylate group,

R^(III3) represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, and

ZA⁺ represents an organic cation.

Examples of the halogen atom represented by R^(III3) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R^(III3) include those which are the same as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R^(a8).

Examples of the alkanediyl group having 1 to 8 carbon atoms represented by A^(x1) include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group and the like.

Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted in A^(X1) include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluorohexyl group and the like.

Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by X^(III3) include a linear or branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, or a combination thereof.

Specific examples thereof include linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group and a dodecane-1,12-diyl group; branched alkanediyl groups such as a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group and a 2-methylbutane-1,4-diyl group;

divalent monocyclic alicyclic saturated hydrocarbon groups, for example, cycloalkanediyl groups such as a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group and a cyclooctane-1,5-diyl group; and divalent polycyclic alicyclic saturated hydrocarbon groups such as a norbornane-1,4-diyl group, a norbornane-2,5-diyl group, an adamantane-1,5-diyl group and an adamantane-2,6-diyl group.

Those in which —CH₂— included in the saturated hydrocarbon group are replaced by —O—, —S— or —CO— include, for example, divalent groups represented by formula (X1) to formula (X53). Before replacing —CH₂— included in the saturated hydrocarbon group by —O—, —S— or —CO—, the number of carbon atoms is 17 or less. In the following formulas, * and ** represent a bonding site, and * represents a bonding site to A^(x1).

X³ represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms.

X⁴ represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms.

X⁵ represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.

X⁶ represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms.

X⁷ represents a trivalent saturated hydrocarbon group having 1 to 14 carbon atoms.

X⁹ represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.

Examples of the organic cation represented by ZA⁺ include an organic onium cation, an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation and an organic phosphonium cation. Of these, an organic sulfonium cation and an organic iodonium cation are preferable, and an aryl sulfonium cation is more preferable. Specific examples thereof include a cation represented by any one of the above-mentioned formula (b2-1) to formula (b2-4) (hereinafter sometimes referred to as “cation (b2-1)” according to the number of formula).

The structural unit represented by formula (II-2-A′) is preferably a structural unit represented by formula (II-2-A):

wherein, in formula (II-2-A),

R^(III3), X^(III3) and ZA⁺ are the same as defined above,

z represents an integer of 0 to 6,

R^(III2) and R^(III4) each independently represent a hydrogen atom, a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms, and when z is 2 or more, a plurality of R^(III2) and R^(III4) may be the same or different form each other, and

Q^(a) and Q^(b) each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.

Examples of the perfluoroalkyl group having 1 to 6 carbon atoms represented by R^(III2), R^(III4), Q^(a) and Q^(b) include those which are the same as the perfluoroalkyl group having 1 to 6 carbon atoms represented by Q^(b1) mentioned below.

The structural unit represented by formula (II-2-A) is preferably a structural unit represented by formula (II-2-A-1):

wherein, in formula (II-2-A-1),

R^(III2), R^(III3), R^(III4), Q^(a), Q^(b), z and ZA⁺ are the same as defined above, R^(III5) represents a saturated hydrocarbon group having 1 to 12 carbon atoms, and

X^(I2) represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, —CH₂— included in the saturated hydrocarbon group may be replaced by —O—, —S— or —CO—, and a hydrogen atom included in the saturated hydrocarbon group may be substituted with a halogen atom or a hydroxy group.

Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by R^(III5) include linear or branched alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group.

Examples of the divalent saturated hydrocarbon group represented by X^(I2) include those which are the same as the divalent saturated hydrocarbon group represented by X^(III3).

The structural unit represented by formula (II-2-A-1) is preferably a structural unit represented by formula (II-2-A-2):

wherein, in formula (II-2-A-2),

R^(III3), R^(III5) and ZA⁺ are the same as defined above, and

m and nA each independently represent 1 or 2.

The structural unit represented by formula (II-2-A′) includes, for example, the following structural units, structural units in which a group corresponding to a methyl group of R^(III3) is substituted with an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom, a halogen atom (e.g., fluorine atom) or a halogen atom (e.g., trifluoromethyl group, etc.) and the structural units mentioned in WO 2012/050015 A. ZA⁺ represents an organic cation.

The structural unit having a sulfonio group and an organic anion in a side chain is preferably a structural unit represented by formula (II-1-1):

wherein, in formula (II-1-1),

A^(II1) represents a single bond or a divalent linking group,

R^(II1) represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms,

R^(II2) and R^(II3) each independently represent a hydrocarbon group having 1 to 18 carbon atoms, and R^(II2) and R^(II3) may be bonded to each other to form a ring together with sulfur atoms to which R^(II2) and R^(II3) are bonded,

R^(II4) represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, and

A⁻ represents an organic anion.

Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R^(II1) include a phenylene group and a naphthylene group.

Examples of the hydrocarbon group represented by R^(II2) and R^(II3) include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and groups obtained by combining these groups.

Examples of the alkyl group and the alicyclic hydrocarbon group include those which are the same as mentioned above.

Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group and a phenanthryl group.

Examples of the combined group include groups obtained by combining the above-mentioned alkyl group and alicyclic hydrocarbon group, aralkyl groups such as a benzyl group, aromatic hydrocarbon groups having an alkyl group (a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having an alicyclic hydrocarbon group (a p-cyclohexylphenyl group, a p-adamantylphenyl group, etc.), aryl-cycloalkyl groups such as a phenylcyclohexyl group, and the like.

Examples of the halogen atom represented by R^(II4) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R^(II4) include those which are the same as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R^(a8).

Examples of the divalent linking group represented by A^(II1) include a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and —CH₂— included in the divalent saturated hydrocarbon group may be replaced by —O—, —S— or —CO—. Specific examples thereof include those which are the same as the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by X^(III3).

Examples of the structural unit including a cation in formula (II-1-1) include the following structural units, structural units in which a group corresponding to a methyl group of R^(II4) is substituted with a hydrogen atom, a halogen atom (e.g., a fluorine atom, etc.) or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom (e.g., a trifluoromethyl group, etc.) and the like.

Examples of the organic anion represented by A⁻ include a sulfonic acid anion, a sulfonylimide anion, a sulfonylmethide anion and a carboxylic acid anion. The organic anion represented by A⁻ is preferably a sulfonic acid anion, and examples of the sulfonic acid anion include those which are the same as an anion in the below-mentioned salt represented by formula (B1).

Examples of the sulfonylimide anion represented by A-include the followings.

Examples of the sulfonylmethide anion include the followings.

Examples of the carboxylic acid anion include the followings.

Examples of the structural unit represented by formula (II-1-1) include the followings.

When the structural unit (II) is included in the resin (A), the content of the structural unit (II) is preferably 1 to 20 mol %, more preferably 2 to 15 mol %, and still more preferably 3 to 10 mol %, based on all structural units of the resin (A).

The resin (A) may include structural units other than the structural units mentioned above, and examples of such structural unit include structural units well-known in the art.

The resin (A) is preferably a resin composed of a structural unit (a1) and a structural unit (s), namely, a copolymer of a monomer (a1) and a monomer (s).

The structural unit (a1) is preferably at least one selected from the group consisting of a structural unit (a1-0), a structural unit (a1-1) and a structural unit (a1-2) (preferably the structural unit having a cyclohexyl group, or a cyclopentyl group), more preferably at least two, and still more preferably at least two selected from the group consisting of a structural unit (a1-1) and a structural unit (a1-2).

The structural unit (s) is preferably at least one selected from the group consisting of a structural unit (a2) and a structural unit (a3). The structural unit (a2) is preferably a structural unit represented by formula (a2-1) or a structural unit represented by formula (a2-A). The structural unit (a3) is preferably at least one selected from the group consisting of a structural unit represented by formula (a3-1), a structural unit represented by formula (a3-2) and a structural unit represented by formula (a3-4).

The respective structural units constituting the resin (A) may be used alone, or two or more structural units may be used in combination. Using a monomer from which these structural units are derived, it is possible to produce by a known polymerization method (e.g. radical polymerization method). The content of the respective structural units included in the resin (A) can be adjusted according to the amount of the monomer used in the polymerization.

The weight-average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, and still more preferably 3,000 or more), and 50,000 or less (more preferably 30,000 or less, and still more preferably 15,000 or less). In the present specification, the weight-average molecular weight is a value determined by gel permeation chromatography under the conditions mentioned in Examples.

<Resin Other than Resin (A)>

The resist composition of the present invention may include resins other than the resin (A).

The resin other than the resin (A) includes, for example, a resin including a structural unit (a4) or a structural unit (a5) (hereinafter sometimes referred to as resin (X)).

The resin (X) is preferably a resin including a structural unit (a4), particularly.

In the resin (X), the content of the structural unit (a4) is preferably 30 mol or more, more preferably 40 mol % or more, and still more preferably 45 mol or more, based on the total of all structural units of the resin (X).

Examples of the structural unit, which may be further included in the resin (X), include a structural unit (a2), a structural unit (a3) and structural units derived from other known monomers. Particularly, the resin (X) is preferably a resin composed only of a structural unit (a4) and/or a structural unit (a5), and more preferably a resin composed only of a structural unit (a4).

The respective structural unit constituting the resin (X) may be used alone, or two or more structural units may be used in combination. Using a monomer from which these structural units are derived, it is possible to produce by a known polymerization method (e.g. radical polymerization method). The content of the respective structural units included in the resin (X) can be adjusted according to the amount of the monomer used in the polymerization.

The weight-average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). The measurement means of the weight-average molecular weight of the resin (X) is the same as in the case of the resin (A).

When the resist composition includes the resin (X), the content is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, still more preferably 1 to 40 parts by mass, yet more preferably 1 to 30 parts by mass, and further preferably 1 to 8 parts by mass, based on 100 parts by mass of the resin (A).

The content of the resin (A) in the resist composition is preferably 80% by mass or more and 99% by mass or less, and more preferably 90% by mass or more and 99% by mass or less, based on the solid component of the resist composition. When including resins other than the resin (A), the total content of the resin (A) and resins other than the resin (A) is preferably 80% by mass or more and 99% by mass or less, and more preferably 90% by mass or more and 99% by mass or less, based on the solid component of the resist composition. The solid content of the resist composition and the content of the resin thereto can be measured by a known analysis means such as liquid chromatography or gas chromatography.

<Acid Generator (B)>

Either nonionic or ionic acid generator may be used as the acid generator (B). Examples of the nonionic acid generator include sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane) and the like. Typical examples of the ionic acid generator include onium salts containing an onium cation (e.g., diazonium salt, phosphonium salt, sulfonium salt, iodonium salt). Examples of the anion of the onium salt include a sulfonic acid anion, a sulfonylimide anion, a sulfonylmethide anion and the like.

Specific examples of the acid generator (B) include compounds generating an acid upon exposure to radiation mentioned in JP 63-26653 A, JP 55-164824 A, JP 62-69263 A, JP 63-146038 A, JP 63-163452 A, JP 62-153853 A, JP 63-146029 A, U.S. Pat. Nos. 3,779,778, 3,849,137, DE Patent No. 3914407 and EP Patent No. 126,712. Compounds produced by a known method may also be used. Two or more acid generators (B) may also be used in combination.

The acid generator (B) is preferably a fluorine-containing acid generator, and more preferably a salt represented by formula (B1) (hereinafter sometimes referred to as “acid generator (B1)”):

wherein, in formula (B1),

Q^(b1) and Q^(b2) each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms,

L^(b1) represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, —CH₂— included in the saturated hydrocarbon group may be replaced by —O— or —CO—, and a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group,

Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and —CH₂— included in the alicyclic hydrocarbon group may be replaced by —O—, —SO₂— or —CO—, and

Z1⁺ represents an organic cation.

Examples of the perfluoroalkyl group represented by Q^(b1) and Q^(b2) include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group and a perfluorohexyl group.

Preferably, Q^(b1) and Q^(b2) are each independently a fluorine atom or a trifluoromethyl group, and more preferably, both are fluorine atoms.

Examples of the divalent saturated hydrocarbon group in L^(b1) include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, or the divalent saturated hydrocarbon group may be a group formed by combining two or more of these groups.

Specific examples thereof include linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1,14-diyl group, a pentadecane-1,15-diyl group, a hexadecane-1,16-diyl group and a heptadecane-1,17-diyl group;

branched alkanediyl groups such as an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group and a 2-methylbutane-1,4-diyl group;

monocyclic divalent alicyclic saturated hydrocarbon groups such as a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group and a cyclooctane-1,5-diyl group; and

polycyclic divalent alicyclic saturated hydrocarbon groups such as a norbornane-1,4-diyl group, a norbornane-2,5-diyl group, an adamantane-1,5-diyl group and an adamantane-2,6-diyl group.

The group in which —CH₂— included in the divalent saturated hydrocarbon group represented by L^(b1) is replaced by —O— or —CO— includes, for example, a group represented by any one of formula (b1-1) to formula (b1-3). In groups represented by formula (b1-1) to formula (b1-3) and groups represented by formula (b1-4) to formula (b1-11) which are specific examples thereof, * and ** represent a bonding site, and * represents a bonding site to —Y.

In formula (b1-1),

L^(b2) represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom,

L^(b3) represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and —CH₂— included in the saturated hydrocarbon group may be replaced by —O— or —CO—, and the total number of carbon atoms of L^(b2) and L^(b3) is 22 or less.

In formula (b1-2),

L^(b4) represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom,

L^(b5) represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and —CH₂— included in the saturated hydrocarbon group may be replaced by —O— or —CO—, and

the total number of carbon atoms of L^(b4) and L^(b5) is 22 or less.

In formula (b1-3),

L^(b6) represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group,

L^(b7) represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and —CH₂— included in the saturated hydrocarbon group may be replaced by —O— or —CO—, and

the total number of carbon atoms of L^(b6) and L^(b7) is 23 or less.

In groups represented by formula (b1-1) to formula (b1-3), when —CH₂— included in the saturated hydrocarbon group is replaced by —O— or —CO—, the number of carbon atoms before replacement is taken as the number of carbon atoms of the saturated hydrocarbon group.

Examples of the divalent saturated hydrocarbon group include those which are the same as the divalent saturated hydrocarbon group of L^(b1).

L^(b2) is preferably a single bond.

L^(b3) is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

L^(b4) is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and a hydrogen atom included in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.

L^(b5) is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.

L^(b6) is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom.

L^(b7) is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and —CH₂— included in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—.

The group in which —CH₂— included in the divalent saturated hydrocarbon group represented by L^(b1) is replaced by —O— or —CO— is preferably a group represented by formula (b1-1) or formula (b1-3).

Examples of the group represented by formula (b1-1) include groups represented by formula (b1-4) to formula (b1-8).

In formula (b1-4),

L^(b8) represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.

In formula (b1-5),

L^(b9) represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and —CH₂— included in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—.

L^(b10) represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and a hydrogen atom included in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and

the total number of carbon atoms of L^(b9) and L^(b10) is 20 or less.

In formula (b1-6),

L^(b11) represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms,

L^(b12) represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom included in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and

the total number of carbon atoms of L^(b11) and L^(b12) is 21 or less.

In formula (b1-7),

L^(b13) represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms,

L^(b14) represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and —CH₂— included in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—,

L^(b15) represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and a hydrogen atom included in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and

the total number of carbon atoms of L^(b13) to L^(b15) is 19 or less.

In formula (b1-8),

L^(b16) represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and —CH₂— included in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—,

L^(b17) represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms,

L^(b18) represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and a hydrogen atom included in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and

the total number of carbon atoms of L^(b16) to L^(b18) is 19 or less.

L^(b8) is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

L^(b9) is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.

L^(b10) is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.

L^(b11) is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.

L^(b12) is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.

L^(b13) is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.

L^(b14) is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms.

L^(b15) is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.

L^(b16) is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.

L^(b17) is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms.

L^(b18) is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

Examples of the group represented by formula (b1-3) include groups represented by formula (b1-9) to formula (b1-11).

In formula (b1-9),

L^(b19) represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom,

L^(b20) represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group, —CH₂— included in the alkylcarbonyloxy group may be replaced by —O— or —CO—, and a hydrogen atom included in the alkylcarbonyloxy group may be substituted with a hydroxy group, and

the total number of carbon atoms of L^(b19) and L^(b20) is 23 or less.

In formula (b1-10),

L^(b21) represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom,

L^(b22) represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms,

L^(b23) represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group, —CH₂— included in the alkylcarbonyloxy group may be replaced by —O— or —CO—, and a hydrogen atom included in the alkylcarbonyloxy group may be substituted with a hydroxy group, and

the total number of carbon atoms of L^(b21), L^(b22) and L^(b23) is 21 or less.

In formula (b1-11),

L^(b24) represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom,

L^(b25) represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms,

L^(b26) represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group, —CH₂— included in the alkylcarbonyloxy group may be replaced by —O— or —CO—, and a hydrogen atom included in the alkylcarbonyloxy group may be substituted with a hydroxy group, and

the total number of carbon atoms of L^(b24), L^(b25) and L^(b26) is 21 or less.

In groups represented by formula (b1-9) to formula (b1-11), when a hydrogen atom included in the saturated hydrocarbon group is substituted with an alkylcarbonyloxy group, the number of carbon atoms before substitution is taken as the number of carbon atoms of the saturated hydrocarbon group.

Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, an adamantylcarbonyloxy group and the like.

Examples of the group represented by formula (b1-4) include the followings:

Examples of the group represented by formula (b1-5) include the followings:

Examples of the group represented by formula (b1-6) include the followings:

Examples of the group represented by formula (b1-7) include the followings:

Examples of the group represented by formula (b1-8) include the followings:

Examples of the group represented by formula (b1-2) include the followings:

Examples of the group represented by formula (b1-9) include the followings:

Examples of the group represented by formula (b1-10) include the followings:

Examples of the group represented by formula (b1-11) include the followings:

Examples of the alicyclic hydrocarbon group represented by Y include groups represented by formula (Y1) to formula (Y11) and formula (Y36) to formula (Y38).

When —CH₂— included in the alicyclic hydrocarbon group represented by Y is replaced by —O—, —SO₂— or —CO—, the number may be 1, or 2 or more. Examples of such group include groups represented by formula (Y12) to formula (Y35) and formula (Y39) to formula (Y43). * represents a bonding site to L^(b1).

The alicyclic hydrocarbon group represented by Y is preferably a group represented by any one of formula (Y1) to formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31) and formula (Y39) to formula (Y43), more preferably a group represented by formula (Y11), formula (Y15), formula (Y16), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43), and still more preferably a group represented by formula (Y11), formula (Y15), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43).

When the alicyclic hydrocarbon group represented by Y is a spiro ring having an oxygen atom, such as formula (Y28) to formula (Y35), formula (Y39), formula (Y40), formula (Y42) or formula (Y43), the alkanediyl group between two oxygen atoms preferably has one or more fluorine atoms. Of alkanediyl groups included in a ketal structure, it is preferable that a methylene group adjacent to the oxygen atom is not substituted with a fluorine atom.

Examples of the substituent of the methyl group represented by Y include a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, a glycidyloxy group, a —(CH₂)_(ja)—CO—O—R^(b1) group or a —(CH₂)_(ja)—O—CO—R^(b1) group (wherein R^(b1) represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group obtained by combining these groups, ja represents an integer of 0 to 4, —CH₂— included in the alkyl group and the alicyclic hydrocarbon group may be replaced by —O—, —SO₂— or —CO—, a hydrogen atom included in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be substituted with a hydroxy group or a fluorine atom).

Examples of the substituent of the alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, an alkyl group having 1 to 16 carbon atoms which may be substituted with a hydroxy group (—CH₂— included in the alkyl group may be replaced by —O— or —CO—), an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, a glycidyloxy group, a —(CH₂)_(ja)—CO—O—R^(b1) group or a —(CH₂)_(ja)—O—CO—R^(b1) group (wherein R^(b1) represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group obtained by combining these groups, ja represents an integer of 0 to 4, —CH₂— included in the alkyl group and the alicyclic hydrocarbon group may be replaced by —O—, —SO₂— or —CO—, a hydrogen atom included in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be substituted with a hydroxy group or a fluorine atom).

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an adamantyl group and the like. The alicyclic hydrocarbon group may have a chain hydrocarbon group, and examples thereof include a methylcyclohexyl group, a dimethylcyclohexyl group and the like. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 12, and more preferably 3 to 10.

Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group and a phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and examples of the aromatic hydrocarbon group which has a chain hydrocarbon group include a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a p-ethylphenyl group, a p-tert-butylphenyl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group and the like, and examples of the aromatic hydrocarbon group which has an alicyclic hydrocarbon group include a p-cyclohexylphenyl group, a p-adamantylphenyl group and the like. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 14, and more preferably 6 to 10.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group and the like. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 4.

Examples of the alkyl group substituted with a hydroxy group include hydroxyalkyl groups such as a hydroxymethyl group and a hydroxyethyl group.

Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and a naphthylethyl group.

Examples of the group in which —CH₂— included in the alkyl group is replaced by —O—, —SO₂— or —CO— include an alkoxy group, an alkylsulfonyl group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, or a group obtained by combining these groups.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and a dodecyloxy group. The number of carbon atoms of the alkoxy group is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 4.

Examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group and the like. The number of carbon atoms of the alkylsulfonyl group is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 4.

Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group and the like. The number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4.

Examples of the alkylcarbonyl group include an acetyl group, a propionyl group and a butyryl group. The number of carbon atoms of the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4.

Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group and the like. The number of carbon atoms of the alkylcarbonyloxy group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4.

Examples of the combined group include a group obtained by combining an alkoxy group with an alkyl group, a group obtained by combining an alkoxy group with an alkoxy group, a group obtained by combining an alkoxy group with an alkylcarbonyl group, a group obtained by combining an alkoxy group with an alkylcarbonyloxy group and the like.

Examples of the group obtained by combining an alkoxy group with an alkyl group include alkoxyalkyl groups such as a methoxymethyl group, a methoxyethyl group, an ethoxyethyl group, an ethoxymethyl group and the like. The number of carbon atoms of the alkoxyalkyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4.

Examples of the group obtained by combining an alkoxy group with an alkoxy group include alkoxyalkoxy groups such as a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group and the like. The number of carbon atoms of the alkoxyalkoxy group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4.

Examples of the group obtained by combining an alkoxy group with an alkylcarbonyl group include alkoxyalkylcarbonyl groups such as a methoxyacetyl group, a methoxypropionyl group, an ethoxyacetyl group, an ethoxypropionyl group and the like. The number of carbon atoms of the alkoxyalkylcarbonyl group is preferably 3 to 13, more preferably 3 to 7, and still more preferably 3 to 5.

Examples of the group obtained by combining an alkoxy group with an alkylcarbonyloxy group include alkoxyalkylcarbonyloxy groups such as a methoxyacetyloxy group, a methoxypropionyloxy group, an ethoxyacetyloxy group, an ethoxypropionyloxy group and the like. The number of carbon atoms of the alkoxyalkylcarbonyloxy group is preferably 3 to 13, more preferably 3 to 7, and still more preferably 3 to 5.

Examples of the group in which —CH₂— included in the alicyclic hydrocarbon group is replaced by —O—, —SO₂— or —CO— include groups represented by formula (Y12) to formula (Y35), formula (Y39) to formula (Y43) and the like.

Examples of Y include the followings.

Y is preferably an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, more preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, still more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and yet more preferably an adamantyl group which may have a substituent, and —CH₂— constituting the alicyclic hydrocarbon group or the adamantyl group may be replaced by —CO—, —SO₂— or —CO—. Specifically, Y is preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group, or groups represented by formula (Y42), formula (Y100) to formula (Y114).

The anion in the salt represented by formula (B1) is preferably anions represented by formula (B1-A-1) to formula (B1-A-59) [hereinafter sometimes referred to as “anion (B1-A-1)” according to the number of formula], and more preferably an anion represented by any one of formula (B1-A-1) to formula (B1-A-4), formula (B1-A-9), formula (B1-A-10), formula (B1-A-24) to formula (B1-A-33), formula (B1-A-36) to formula (B1-A-40) and formula (B1-A-47) to formula (B1-A-59).

R^(i2) to R^(i7) each independently represent, for example, an alkyl group having 1 to 4 carbon atoms, and preferably a methyl group or an ethyl group. R^(i8) is, for example, a chain hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or groups formed by combining these groups, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. L^(A41) is a single bond or an alkanediyl group having 1 to 4 carbon atoms. Q^(b1) and Q^(b2) are the same as defined above.

Specific examples of the anion in the salt represented by formula (B1) include anions mentioned in JP 2010-204646 A.

Examples of anions in the salt represented by formula (B1) preferably include anions each represented by formula (B1a-1) to formula (B1a-38).

Of these, an anion represented by any one of formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula (B1a-16), formula (B1a-18), formula (B1a-19) and formula (B1a-22) to formula (B1a-38) is preferable.

Examples of the organic cation as for Z1⁺ include an organic onium cation, an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation and an organic phosphonium cation. Of these, an organic sulfonium cation and an organic iodonium cation are preferable, and an arylsulfonium cation is more preferable. Examples of the arylsulfonium cation include those which are the same as the cation as for Z⁺ in formula (I).

The acid generator (B) is a combination of the anion mentioned above and the organic cation mentioned above, and these can be optionally combined. The acid generator (B) preferably includes a combination of an anion represented by any one of formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula (B1a-16), formula (B1a-18), formula (B1a-19) and formula (B1a-22) to formula (B1a-38) with a cation (b2-1), a cation (b2-3) or a cation (b2-4).

The acid generator (B) preferably includes those represented by formula (B1-1) to formula (B1-57). Of these acid generators, those containing an arylsulfonium cation are preferable and those represented by formula (B1-1) to formula (B1-3), formula (B1-5) to formula (B1-7), formula (B1-11) to formula (B1-14), formula (B1-20) to formula (B1-26), formula (B1-29) and formula (B1-31) to formula (B1-57) are particularly preferable.

In the resist composition of the present invention, the content of the acid generator is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 1 part by mass or more and 45 parts by mass or less, and still more preferably 3 parts by mass or more and 40 parts by mass or less, based on 100 parts by mass of the resin (A).

<Solvent (E)>

The content of the solvent (E) in the resist composition is usually 90% by mass or more and 99.9% by mass or less, preferably 92% by mass or more and 99, by mass or less, and more preferably 94% by mass or more and 99% by mass or less. The content of the solvent (E) can be measured, for example, by a known analysis means such as liquid chromatography or gas chromatography.

Examples of the solvent (E) include glycol ether esters such as ethylcellosolve acetate, methylcellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; and cyclic esters such as γ-butyrolactone. The solvent (E) may be used alone, or two or more solvents may be used.

<Quencher (C)>

Examples of the quencher (C) include a salt generating an acid having an acidity lower than that of an acid generated from an acid generator (B), and a basic nitrogen-containing organic compound. The content of the quencher (C) is preferably about 0.01 to 15% by mass, more preferably about 0.01 to 10% by mass, still more preferably about 0.1 to 8% by mass, and yet more preferably about 0.1 to 7% by mass, based on the amount of the solid component of the resist composition.

<Salt Generating an Acid Having an Acidity Lower than that of an Acid Generated from the Acid Generator>

The acidity in a salt generating an acid having an acidity lower than that of an acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). Regarding the salt generating an acid having an acidity lower than that of an acid generated from the acid generator (B), the acid dissociation constant of an acid generated from the salt usually meets the following inequality: −3<pKa, preferably −1<pKa<7, and more preferably 0<pKa<5.

Examples of the salt generating an acid having an acidity lower than that of an acid generated from the acid generator (B) include salts represented by the following formulas, a salt represented by formula (D) mentioned in JP 2015-147926 A (hereinafter sometimes referred to as “weak acid inner salt (D)”, and salts mentioned in JP 2012-229206 A, JP 2012-6908 A, JP 2012-72109 A, JP 2011-39502 A and JP 2011-191745 A. The salt generating an acid having an acidity lower than that of an acid generated from the acid generator (B) is preferably a salt generating a carboxylic acid having an acidity lower than that of an acid generated from the acid generator (B) (salt having a carboxylic acid anion), and more preferably a weak acid inner salt (D), and still more preferably a diphenyliodonium salt containing a phenyl group substituted with a carboxylic acid anion among the weak acid inner salt (D).

Examples of the weak acid inner salt (D) is preferably a diphenyliodonium salt having an iodonium cation to which two phenyl groups are bonded, and a carboxylic acid anion substituted with at least one phenyl group of two phenyl groups bonded to the iodonium cation, and specific examples thereof include a salt represented by the following formula:

wherein, in formula (D),

R^(D1) and R^(D2) each independently represent a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 7 carbon atoms, an acyloxy group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a nitro group or a halogen atom, and

m′ and n′ each independently represent an integer of 0 to 4, and when m′ is 2 or more, a plurality of R^(D1) may be the same or different, and when n′ is 2 or more, a plurality of R^(D2) may be the same or different.

Examples of the hydrocarbon group as for R^(D1) and R^(D2) include a chain hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these groups.

Examples of the chain hydrocarbon group include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a nonyl group and the like.

The alicyclic hydrocarbon group may be either monocyclic or polycyclic, or may be either saturated or unsaturated. Examples thereof include cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclononyl group and a cyclododecyl group, a norbornyl group, an adamantyl group and the like.

Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, a 4-propylphenyl group, a 4-isopropylphenyl group, a 4-butylphenyl group, a 4-t-butylphenyl group, a 4-hexylphenyl group, a 4-cyclohexylphenyl group, an anthryl group, a p-adamantylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a biphenyl group, a phenanthryl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl and the like.

Examples of the group formed by combining these groups include an alkyl-cycloalkyl group, a cycloalkyl-alkyl group, an aralkyl group (e.g., a phenylmethyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 1-phenyl-1-propyl group, a 1-phenyl-2-propyl group, a 2-phenyl-2-propyl group, a 3-phenyl-1-propyl group, a 4-phenyl-1-butyl group, a 5-phenyl-1-pentyl group, a 6-phenyl-1-hexyl group, etc.) and the like.

Examples of the alkoxy group include a methoxy group, an ethoxy group and the like.

Examples of the acyl group include an acetyl group, a propanoyl group, a benzoyl group, a cyclohexanecarbonyl group and the like.

Examples of the acyloxy group include a group obtained by bonding an oxy group (—O—) to the above acyl group.

Examples of the alkoxycarbonyl group include a group obtained by bonding a carbonyl group (—CO—) to the above alkoxy group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like.

Preferably, R^(D1) and R^(D2) each independently represent an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, a nitro group or a halogen atom.

Preferably, m′ and n′ are each independently an integer of 0 to 2, and more preferably 0, and when m′ is 2 or more, a plurality of R^(D1) may be the same or different, and when n′ is 2 or more, a plurality of R^(D2) may be the same or different.

More specifically, the following salts are exemplified.

Examples of the basic nitrogen-containing organic compound include amine and an ammonium salt. Examples of the amine include an aliphatic amine and an aromatic amine. Examples of the aliphatic amine include a primary amine, a secondary amine and a tertiary amine.

Examples of the amine include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diamino-1,2-diphenylethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, 2,2′-methylenebisaniline, imidazole, 4-methylimidazole, pyridine, 4-methylpyridine, 1,2-di(2-pyridyl)ethane, 1,2-di(4-pyridyl)ethane, 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di(2-pyridyl)ketone, 4,4′-dipyridyl sulfide, 4,4′-dipyridyl disulfide, 2,2′-dipyridylamine, 2,2′-dipicolylamine, bipyridine and the like, preferably aromatic amines such as diisopropylaniline, and more preferably 2,6-diisopropylaniline.

Examples of the ammonium salt include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra-n-butylammonium salicylate and choline.

<Other Components>

The resist composition of the present invention may also include components other than the components mentioned above (hereinafter sometimes referred to as “other components (F)”). The other components (F) are not particularly limited and it is possible to use various additives known in the resist field, for example, sensitizers, dissolution inhibitors, surfactants, stabilizers and dyes.

<Preparation of Resist Composition>

The resist composition of the present invention can be prepared by mixing a carboxylate (I), a resin (A) and an acid generator (B), and if necessary, resins other than the resin (A), a solvent (E), a quencher (C) and other components (F). The order of mixing these components is any order and is not particularly limited. It is possible to select, as the temperature during mixing, appropriate temperature from 10 to 40° C., according to the type of the resin, the solubility in the solvent (E) of the resin and the like. It is possible to select, as the mixing time, appropriate time from 0.5 to 24 hours according to the mixing temperature. The mixing means is not particularly limited and it is possible to use mixing with stirring.

After mixing the respective components, the mixture is preferably filtered through a filter having a pore diameter of about 0.003 to 0.2 μm.

(Method for Producing Resist Pattern)

The method for producing a resist pattern of the present invention include:

(1) a step of applying the resist composition of the present invention on a substrate, (2) a step of drying the applied composition to form a composition layer, (3) a step of exposing the composition layer, (4) a step of heating the exposed composition layer, and (5) a step of developing the heated composition layer.

The resist composition can be usually applied on a substrate using a conventionally used apparatus, such as a spin coater. Examples of the substrate include inorganic substrates such as a silicon wafer, and organic substrates in which a resist film is formed on a surface. Before applying the resist composition, the substrate may be washed, and an organic antireflection film may be formed on the substrate.

The solvent is removed by drying the applied composition to form a composition layer. Drying is performed by evaporating the solvent using a heating device such as a hot plate (so-called “prebake”), or a decompression device. The heating temperature is preferably 50 to 200° C. and the heating time is preferably 10 to 180 seconds. The pressure during drying under reduced pressure is preferably about 1 to 1.0×10⁵ Pa.

The composition layer thus obtained is usually exposed using an aligner. The aligner may be a liquid immersion aligner. It is possible to use, as an exposure source, various exposure sources, for example, exposure sources capable of emitting laser beam in an ultraviolet region such as KrF excimer laser (wavelength of 248 nm), ArF excimer laser (wavelength of 193 nm) and F2 excimer laser (wavelength of 157 nm), an exposure source capable of emitting harmonic laser beam in a far-ultraviolet or vacuum ultra violet region by wavelength-converting laser beam from a solid-state laser source (YAG or semiconductor laser), an exposure source capable of emitting electron beam or EUV and the like. In the present specification, such exposure to radiation is sometimes collectively referred to as “exposure”. The exposure is usually performed through a mask corresponding to a pattern to be required. When electron beam is used as the exposure source, exposure may be performed by direct writing without using the mask.

The exposed composition layer is subjected to a heat treatment (so-called “post-exposure bake”) to promote the deprotection reaction in an acid-labile group. The heating temperature is usually about 50 to 200° C., and preferably about 70 to 150° C. It is also possible to perform a chemical treatment (silylation) which adjusts the hydrophilicity or hydrophobicity of the resin on a surface side of the composition after heating. Before performing the development, the steps of application of the resist composition, drying, exposure and heating may be repeatedly performed on the exposed composition layer.

The heated composition layer is usually developed with a developing solution using a development apparatus. Examples of the developing method include a dipping method, a paddle method, a spraying method, a dynamic dispensing method and the like. The developing temperature is preferably, for example, 5 to 60° C. and the developing time is preferably, for example, 5 to 300 seconds. It is possible to produce a positive resist pattern or negative resist pattern by selecting the type of the developing solution as follows.

When the positive resist pattern is produced from the resist composition of the present invention, an alkaline developing solution is used as the developing solution. The alkaline developing solution may be various aqueous alkaline solutions used in this field. Examples thereof include aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline). The surfactant may be contained in the alkaline developing solution.

It is preferable that the developed resist pattern is washed with ultrapure water and then water remaining on the substrate and the pattern is removed.

When the negative resist pattern is produced from the resist composition of the present invention, a developing solution containing an organic solvent (hereinafter sometimes referred to as “organic developing solution”) is used as the developing solution.

Examples of the organic solvent contained in the organic developing solution include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycol ether solvents such as propylene glycol monomethyl ether; amide solvents such as N,N-dimethylacetamide; and aromatic hydrocarbon solvents such as anisole.

The content of the organic solvent in the organic developing solution is preferably 90% by mass or more and 100%. by mass or less, more preferably 95% by mass or more and 100% by mass or less, and still more preferably the organic developing solution is substantially composed of the organic solvent.

Particularly, the organic developing solution is preferably a developing solution containing butyl acetate and/or 2-heptanone. The total content of butyl acetate and 2-heptanone in the organic developing solution is preferably 50% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100, by mass or less, and still more preferably the organic developing solution is substantially composed of butyl acetate and/or 2-heptanone.

The surfactant may be contained in the organic developing solution. A trace amount of water may be contained in the organic developing solution.

During development, the development may be stopped by replacing by a solvent with the type different from that of the organic developing solution.

The developed resist pattern is preferably washed with a rinsing solution. The rinsing solution is not particularly limited as long as it does not dissolve the resist pattern, and it is possible to use a solution containing an ordinary organic solvent which is preferably an alcohol solvent or an ester solvent.

After washing, the rinsing solution remaining on the substrate and the pattern is preferably removed.

(Applications)

The resist composition of the present invention is suitable as a resist composition for exposure of KrF excimer laser, a resist composition for exposure of ArF excimer laser, a resist composition for exposure of electron beam (EB) or a resist composition for exposure of EUV, particularly a resist composition for exposure of electron beam (EB) or a resist composition for exposure of EUV, and the resist composition is useful for fine processing of semiconductors.

EXAMPLES

The present invention will be described more specifically by way of Examples. Percentages and parts expressing the contents or amounts used in the Examples are by mass unless otherwise specified.

The weight-average molecular weight is a value determined by gel permeation chromatography. Analysis conditions of gel permeation chromatography are as follows.

Column: TSKgel Multipore HXL-M×3+guardcolumn (manufactured by TOSOH CORPORATION)

Eluent: tetrahydrofuran

Flow rate: 1.0 mL/min

Detector: RI detector

Column temperature: 40° C.

Injection amount: 100 μl

Molecular weight standards: polystyrene standard (manufactured by TOSOH CORPORATION)

Structures of compounds were confirmed by measuring a molecular ion peak using mass spectrometry (Liquid Chromatography: Model 1100, manufactured by Agilent Technologies, Inc., Mass Spectrometry: Model LC/MSD, manufactured by Agilent Technologies, Inc.). The value of this molecular ion peak in the following Examples is indicated by “MASS”.

Example 1: Synthesis of Salt Represented by Formula (I-1)

4.02 Parts of a carboxylate represented by formula (I-1-a), 2.20 parts of a compound represented by formula (I-1-b) and 20 parts of dimethylformamide were mixed, followed by stirring at 23° C. for 30 minutes. To the mixture thus obtained, 0.88 part of potassium carbonate was added, followed by stirring at 23° C. for 30 minutes and further stirring at 90° C. for 3 hours. The mixture thus obtained was cooled to 23° C. and then 50 parts of chloroform and 20 parts of ion-exchanged water were added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. To the organic layer thus obtained, 20 parts of an aqueous 5 oxalic acid solution was added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. To the organic layer thus obtained, 20 parts of ion-exchanged water was added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. This water washing operation was repeated five times. The organic layer thus obtained was concentrated and then 30 parts of tert-butyl methyl ether was added to the concentrated residue, and after stirring at 23° C. for 30 minutes, the supernatant was removed, followed by concentration to obtain 5.12 parts of a carboxylate represented by formula (I-1).

MASS (ESI (+) Spectrum): M⁺ 263.1

MASS (ESI (−) Spectrum): M⁻ 339.0

Example 2: Synthesis of Salt Represented by Formula (I-16)

4.18 Parts of a carboxylate represented by formula (I 16-a), 2.20 parts of a compound represented by formula (I-1-b) and 20 parts of dimethylformamide were mixed, followed by stirring at 23° C. for 30 minutes. To the mixture thus obtained, 0.88 part of potassium carbonate was added, followed by stirring at 23° C. for 30 minutes and further stirring at 90° C. for 3 hours. The mixture thus obtained was cooled to 23° C. and then 50 parts of chloroform and 20 parts of ion-exchanged water were added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. To the organic layer thus obtained, 20 parts of an aqueous 5% oxalic acid solution was added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. To the organic layer thus obtained, 20 parts of ion-exchanged water was added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. This water washing operation was repeated five times. The organic layer thus obtained was concentrated and then 30 parts of tert-butyl methyl ether was added to the concentrated residue, and after stirring at 23° C. for 30 minutes, the supernatant was removed, followed by concentration to obtain 4.89 parts of a carboxylate represented by formula (I-16).

MASS (ESI (+) Spectrum): M⁺ 263.1

MASS (ESI (−) Spectrum): M⁻ 355.0

Example 3: Synthesis of Salt Represented by Formula (I-17)

4.18 Parts of a carboxylate represented by formula (I-16-a), 4.72 parts of a compound represented by formula (I-17-b) and 20 parts of dimethylformamide were mixed, followed by stirring at 23° C. for 30 minutes. To the mixture thus obtained, 0.88 part of potassium carbonate was added, followed by stirring at 23° C. for 30 minutes and further stirring at 90° C. for 3 hours. The mixture thus obtained was cooled to 23° C. and then 50 parts of chloroform and 20 parts of ion-exchanged water were added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. To the organic layer thus obtained, 20 parts of an aqueous 5% oxalic acid solution was added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. To the organic layer thus obtained, 20 parts of ion-exchanged water was added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. This water washing operation was repeated five times. The organic layer thus obtained was concentrated and then 30 parts of tert-butyl methyl ether was added to the concentrated residue, and after stirring at 23° C. for 30 minutes, the supernatant was removed, followed by concentration to obtain 3.21 parts of a carboxylate represented by formula (I-17).

MASS (ESI (+) Spectrum): M⁺ 263.1

MASS (ESI (−) Spectrum): M⁻ 606.7

Example 4: Synthesis of Salt Represented by Formula (I-26)

4.18 Parts of a carboxylate represented by formula (I-16-a), 1.82 parts of a compound represented by formula (I-26-b) and 20 parts of dimethylformamide were mixed, followed by stirring at 23° C. for 30 minutes. To the mixture thus obtained, 0.88 part of potassium carbonate was added, followed by stirring at 23° C. for 30 minutes and further stirring at 90° C. for 3 hours. The mixture thus obtained was cooled to 23° C. and then 50 parts of chloroform and 20 parts of ion-exchanged water were added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. To the organic layer thus obtained, 20 parts of an aqueous 5% oxalic acid solution was added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. To the organic layer thus obtained, 20 parts of ion-exchanged water was added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. This water washing operation was repeated five times. The organic layer thus obtained was concentrated and then 30 parts of tert-butyl methyl ether was added to the concentrated residue, and after stirring at 23° C. for 30 minutes, the supernatant was removed, followed by concentration to obtain 1.88 parts of a carboxylate represented by formula (I-26).

MASS (ESI (+) Spectrum): M⁺ 263.1

MASS (ESI (−) Spectrum): M⁻ 317.0

Example 5: Synthesis of Salt Represented by Formula (I-389)

4.02 Parts of a carboxylate represented by formula (I-1-a), 3.62 parts of a compound represented by formula (I-389-b) and 20 parts of dimethylformamide were mixed, followed by stirring at 23° C. for 30 minutes. To the mixture thus obtained, 0.88 part of potassium carbonate was added, followed by stirring at 23° C. for 30 minutes and further stirring at 90° C. for 3 hours. The mixture thus obtained was cooled to 23° C. and then 50 parts of chloroform and 20 parts of ion-exchanged water were added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. To the organic layer thus obtained, 20 parts of an aqueous 5% oxalic acid solution was added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. To the organic layer thus obtained, 20 parts of ion-exchanged water was added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. This water washing operation was repeated five times. The organic layer thus obtained was concentrated and then 30 parts of tert-butyl methyl ether was added to the concentrated residue, and after stirring at 23° C. for 30 minutes, the supernatant was removed, followed by concentration to obtain 6.88 parts of a carboxylate represented by formula (I-389).

MASS (ESI (+) Spectrum): M⁺ 263.1

MASS (ESI (−) Spectrum): M⁻ 480.8

Example 6: Synthesis of Salt Represented by Formula (I-390)

4.02 Parts of a carboxylate represented by formula (I-1-a), 3.62 parts of a compound represented by formula (I-390-b) and 20 parts of dimethylformamide were mixed, followed by stirring at 23° C. for 30 minutes. To the mixture thus obtained, 0.88 part of potassium carbonate was added, followed by stirring at 23° C. for 30 minutes and further stirring at 90° C. for 3 hours. The mixture thus obtained was cooled to 23° C. and then 50 parts of chloroform and 20 parts of ion-exchanged water were added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. To the organic layer thus obtained, 20 parts of an aqueous 55 oxalic acid solution was added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. To the organic layer thus obtained, 20 parts of ion-exchanged water was added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. This water washing operation was repeated five times. The organic layer thus obtained was concentrated and then 30 parts of tert-butyl methyl ether was added to the concentrated residue, and after stirring at 23° C. for 30 minutes, the supernatant was removed, followed by concentration to obtain 6.69 parts of a carboxylate represented by formula (I-390).

MASS (ESI (+) Spectrum): M⁺ 263.1

MASS (ESI (−) Spectrum): M⁻ 480.8

Example 7: Synthesis of Salt Represented by Formula (I-393)

4.18 Parts of a carboxylate represented by formula (I-16-a), 3.62 parts of a compound represented by formula (I-389-b) and 20 parts of dimethylformamide were mixed, followed by stirring at 23° C. for 30 minutes. To the mixture thus obtained, 0.88 part of potassium carbonate was added, followed by stirring at 23° C. for 30 minutes and further stirring at 90° C. for 3 hours. The mixture thus obtained was cooled to 23° C. and then 50 parts of chloroform and 20 parts of ion-exchanged water were added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. To the organic layer thus obtained, 20 parts of an aqueous 5, oxalic acid solution was added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. To the organic layer thus obtained, 20 parts of ion-exchanged water was added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. This water washing operation was repeated five times. The organic layer thus obtained was concentrated and then 30 parts of tert-butyl methyl ether was added to the concentrated residue, and after stirring at 23° C. for 30 minutes, the supernatant was removed, followed by concentration to obtain 6.38 parts of a carboxylate represented by formula (I-393).

MASS (ESI (+) Spectrum): M⁺ 263.1

MASS (ESI (−) Spectrum): M⁻ 496.8

Example 8: Synthesis of Salt Represented by Formula (I-394)

4.18 Parts of a carboxylate represented by formula (I-16-a), 3.62 parts of a compound represented by formula (I-390-b) and 20 parts of dimethylformamide were mixed, followed by stirring at 23° C. for 30 minutes. To the mixture thus obtained, 0.88 part of potassium carbonate was added, followed by stirring at 23° C. for 30 minutes and further stirring at 90° C. for 3 hours. The mixture thus obtained was cooled to 23° C. and then 50 parts of chloroform and 20 parts of ion-exchanged water were added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. To the organic layer thus obtained, 20 parts of an aqueous 5′% oxalic acid solution was added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. To the organic layer thus obtained, 20 parts of ion-exchanged water was added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. This water washing operation was repeated five times. The organic layer thus obtained was concentrated and then 30 parts of tert-butyl methyl ether was added to the concentrated residue, and after stirring at 23° C. for 30 minutes, the supernatant was removed, followed by concentration to obtain 6.02 parts of a carboxylate represented by formula (I-394).

MASS (ESI (+) Spectrum): M⁺ 263.1

MASS (ESI (−) Spectrum): M⁻ 496.8

Example 9: Synthesis of Salt Represented by Formula (I-700)

6.80 Parts of a carboxylate represented by formula (I-700-a), 3.62 parts of a compound represented by formula (I-390-b) and 20 parts of dimethylformamide were mixed, followed by stirring at 23° C. for 30 minutes. To the mixture thus obtained, 0.88 part of potassium carbonate was added, followed by stirring at 23° C. for 30 minutes and further stirring at 90° C. for 3 hours. The mixture thus obtained was cooled to 23° C. and then 50 parts of chloroform and 20 parts of ion-exchanged water were added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. To the organic layer thus obtained, 20 parts of an aqueous 5, oxalic acid solution was added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. To the organic layer thus obtained, 20 parts of ion-exchanged water was added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. This water washing operation was repeated five times. The organic layer thus obtained was concentrated and then 30 parts of tert-butyl methyl ether was added to the concentrated residue, and after stirring at 23° C. for 30 minutes, the supernatant was removed, followed by concentration to obtain 8.36 parts of a carboxylate represented by formula (I-700).

MASS (ESI (+) Spectrum): M⁺ 525.0

MASS (ESI (−) Spectrum): M⁻ 496.8

Example 10: Synthesis of Salt Represented by Formula (I-754)

6.36 Parts of a carboxylate represented by formula (I-754-a), 3.62 parts of a compound represented by formula (I-390-b) and 20 parts of dimethylformamide were mixed, followed by stirring at 23° C. for 30 minutes. To the mixture thus obtained, 0.88 part of potassium carbonate was added, followed by stirring at 23° C. for 30 minutes and further stirring at 90° C. for 3 hours. The mixture thus obtained was cooled to 23° C. and then 50 parts of chloroform and 20 parts of ion-exchanged water were added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. To the organic layer thus obtained, 20 parts of an aqueous 5% oxalic acid solution was added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. To the organic layer thus obtained, 20 parts of ion-exchanged water was added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. This water washing operation was repeated five times. The organic layer thus obtained was concentrated and then 30 parts of tert-butyl methyl ether was added to the concentrated residue, and after stirring at 23° C. for 30 minutes, the supernatant was removed, followed by concentration to obtain 7.91 parts of a carboxylate represented by formula (I-754).

MASS (ESI (+) Spectrum): M⁺ 481.0

MASS (ESI (−) Spectrum): M⁻ 496.8

Synthesis of Resin

Compounds (monomers) used in synthesis of a resin (A) are shown below. Hereinafter, these compounds are referred to as “monomer (a1-2-6)” according to the formula number.

Synthesis Example 1 [Synthesis of Resin A1]

Using a monomer (a1-2-6), a monomer (a2-1-3), a monomer (a3-4-2) and a monomer (a1-4-2) as monomers, these monomers were mixed in a molar ratio of 53:3:12:32 [monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-2)], and then this monomer mixture was mixed with methyl isobutyl ketone in the amount of 1.5 mass times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) as initiators were added in the amounts of 1.2 mol % and 3.6 mol based on the total molar number of all monomers, followed by heating at 73° C. for about 5 hours. Thereafter, to the polymerization reaction solution thus obtained, an aqueous p-toluenesulfonic acid solution (2.5% by weight) was added in the amount of 2.0 mass times the total mass of all monomers, followed by stirring for 12 hours and further isolation through separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, followed by filtration and recovery to obtain a resin A1 having a weight-average molecular weight of about 5.3×10³ in a yield of 88%. This resin A1 has the following structural units.

Synthesis Example 2 [Synthesis of Resin A2]

Using a monomer (a1-2-6), a monomer (a2-1-3), a monomer (a3-4-2) and a monomer (a1-4-13) as monomers, these monomers were mixed in a molar ratio of 53:3:12:32 [monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-13)], and then this monomer mixture was mixed with methyl isobutyl ketone in the amount of 1.5 mass times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) as initiators were added in the amounts of 1.2 mol % and 3.6 mol % based on the total molar number of all monomers, followed by heating at 73° C. for about 5 hours. Thereafter, to the polymerization reaction solution thus obtained, an aqueous p-toluenesulfonic acid solution (2.5% by weight) was added in the amount of 2.0 mass times the total mass of all monomers, followed by stirring for 12 hours and further isolation through separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, followed by filtration and recovery to obtain a resin A2 having a weight-average molecular weight of about 5.1×10³ in a yield of 79%. This resin A2 has the following structural units.

<Preparation of Resist Composition>

As shown in Table 2, the following components were mixed and the mixture thus obtained was filtered through a fluororesin filter having a pore diameter of 0.2 μm to prepare resist compositions.

TABLE 2 Resist Acid Carboxylate Quencher composition Resin generator (B) (I) (C) PB/PEB Composition 1 A1 = B1-25= I-1 = — 100° C./130° C. 10 parts 3.4 parts 0.7 part Composition 2 A2 = B1-25 = I-1 = — 100° C./130° C. 10 parts 3.4 parts 0.7 part Composition 3 A1 = B1-25 = I-16 = — 100° C./130° C. 10 parts 3.4 parts 0.7 part Composition 4 A2 = B1-25 = I-16 = — 100° C./130° C. 10 parts 3.4 parts 0.7 part Composition 5 A1 = B1-25 = I-17 = — 100° C./130° C. 10 parts 3.4 parts 0.7 part Composition 6 A2 = B1-25 = I-17 = — 100° C./130° C. 10 parts 3.4 parts 0.7 part Composition 7 A1 = B1-25 = I-26 = — 100° C./130° C. 10 parts 3.4 parts 0.7 part Composition 8 A2 = B1-25 = I-26 = — 100° C./130° C. 10 parts 3.4 parts 0.7 part Composition 9 A1 = B1-25 = I-389 = — 100° C./130° C. 10 parts 3.4 parts 0.7 part Composition 10 A2 = B1-25 = I-389 = — 100° C./130° C. 10 parts 3.4 parts 0.7 part Composition 11 A1 = B1-25 = I-390 = — 100° C./130° C. 10 parts 3.4 parts 0.7 part Composition 12 A2 = B1-25 = I-390 = — 100° C./130° C. 10 parts 3.4 parts 0.7 part Composition 13 A1 = B1-25 = I-393 = — 100° C./130° C. 10 parts 3.4 parts 0.7 part Composition 14 A2 = B1-25 = I-393 = — 100° C./130° C. 10 parts 3.4 parts 0.7 part Composition 15 A1 = B1-25 = I-394 = — 100° C./130° C. 10 parts 3.4 parts 0.7 part Composition 16 A2 = B1-25 = I-394 = — 100° C./130° C. 10 parts 3.4 parts 0.7 part Composition 17 A1 = B1-25 = I-700 = — 100° C./130° C. 10 parts 3.4 parts 0.7 part Composition 18 A2 = B1-25 = I-700 = — 100° C./130° C. 10 parts 3.4 parts 0.7 part Composition 19 A1 = B1-25 = I-754 = — 100° C./130° C. 10 parts 3.4 parts 0.7 part Composition 20 A2 = B1-25 = I-754 = — 100° C./130° C. 10 parts 3.4 parts 0.7 part Comparative A1 = B1-25 = — IX-1 = 100° C./130° C. Composition 1 10 parts 3.4 parts 0.7 part Comparative A1 = B1-25 = — IX-2 = 100° C./130° C. Composition 2 10 parts 3.4 parts 0.7 part Comparative A1 = B1-25 = — IX-3 = 100° C./130° C. Composition 3 10 parts 3.4 parts 0.7 part Comparative A1 = B1-25 = — IX-4 = 100° C./130° C. Composition 4 10 parts 3.4 parts 0.7 part

<Resin>

A1, A2: Resin A1, Resin A2

<Acid Generator (B)>

B1-25: Salt represented by formula (B1-25); synthesized by the method mentioned in JP 2011-126869 A

<Carboxylate (I)>

I-1: Salt represented by formula (I-1)

I-16: Salt represented by formula (I-16)

I-17: Salt represented by formula (I-17)

I-26: Salt represented by formula (I-26)

I-389: Salt represented by formula (I-389)

I-390: Salt represented by formula (I-390)

I-393: Salt represented by formula (I-393)

I-394: Salt represented by formula (I-394)

I-700: Salt represented by formula (I-700)

I-754: Salt represented by formula (I-754)

<Quencher (C)>

IX-1

IX-2

IX-3

IX-4

<Solvent>

Propylene glycol monomethyl ether acetate 400 parts

Propylene glycol monomethyl ether 100 parts

γ-Butyrolactone 5 parts

(Evaluation of Exposure of Resist Composition with Electron Beam)

Each 6 inch-diameter silicon wafer was treated with hexamethyldisilazane on a direct hot plate at 90° C. for 60 seconds. A resist composition was spin-coated on the silicon wafer in such a manner that the thickness of the composition layer became 0.04 μm. Then, the coated silicon wafer was prebaked on the direct hot plate at the temperature shown in the column “PB” of Table 2 for 60 seconds to form a composition layer. Using an electron-beam direct-write system (“ELS-F125 125 keV”, manufactured by ELIONIX INC.), contact hole patterns (hole pitch of 40 nm/hole diameter of 17 nm) were directly written on the composition layer formed on the wafer while changing the exposure dose stepwise.

After exposure, post-exposure baking was performed on the hot plate at the temperature shown in the column “PEB” of Table 2 for 60 seconds. Next, the composition layer on this silicon wafer was developed with butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developing solution at 23° C. for 20 seconds by the dynamic dispense method to obtain a resist pattern.

In the resist pattern obtained after development, the exposure dose at which the diameter of holes formed became 17 nm was regarded as effective sensitivity.

<Evaluation of CD Uniformity (CDU)>

In the effective sensitivity, the hole diameter of the pattern formed with a hole dimeter of 17 nm was determined by measuring 24 times per one hole and the average of the measured values was regarded as the average hole diameter. The standard deviation was determined under the conditions that the average diameter of 400 holes about the patterns formed with a hole dimeter of 17 nm in the same wafer was regarded to as population.

The results are shown in Table 3. The numerical value in the table represents the standard deviation (nm).

TABLE 3 Resist composition CDU Example 11 Composition 1 2.56 Example 12 Composition 2 2.51 Example 13 Composition 3 2.46 Example 14 Composition 4 2.38 Example 15 Composition 5 2.50 Example 16 Composition 6 2.42 Example 17 Composition 7 2.53 Example 18 Composition 8 2.47 Example 19 Composition 9 2.44 Example 20 Composition 10 2.36 Example 21 Composition 11 2.42 Example 22 Composition 12 2.32 Example 23 Composition 13 2.35 Example 24 Composition 14 2.27 Example 25 Composition 15 2.33 Example 26 Composition 16 2.24 Example 27 Composition 17 2.23 Example 28 Composition 18 2.18 Example 29 Composition 19 2.24 Example 30 Composition 20 2.20 Comparative Example 1 Comparative Composition 1 2.68 Comparative Example 2 Comparative Composition 2 2.70 Comparative Example 3 Comparative Composition 3 2.62 Comparative Example 4 Comparative Composition 4 2.63

As compared with Comparative Compositions 1 to 4, Compositions 1 to 20 exhibited small standard deviation and satisfactory evaluation of CD uniformity (CDU).

A resist composition including a carboxylate of the present invention has satisfactory CD uniformity (CDU), and is therefore useful for fine processing of semiconductors. 

1. A carboxylate represented by formula (I):

wherein, in formula (I), Ar represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, X¹ represents an oxygen atom or a sulfur atom, R² represents a halogen atom or a haloalkyl group having 1 to 12 carbon atoms, R² represents a halogen atom, a hydroxy group, a haloalkyl group having 1 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and —CH₂— included in the haloalkyl group and the alkyl group may be replaced by —O— or —CO—, m1 represents an integer of 1 to 6, and when m1 is 2 or more, a plurality of groups in parentheses may be the same or different from each other, m2 represents an integer of 0 to 4, and when m2 is 2 or more, a plurality of R² may be the same or different from each other, and Z⁺ represents an organic cation.
 2. The carboxylate according to claim 1, wherein Ar is an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent.
 3. The carboxylate according to claim 1, wherein X¹ is an oxygen atom.
 4. The carboxylate according to claim 1, wherein R¹ is an iodine atom, a fluorine atom or a perfluoroalkyl group having 1 to 3 carbon atoms.
 5. The carboxylate according to claim 1, wherein R² is an iodine atom, a fluorine atom, a hydroxy group, a perfluoroalkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.
 6. A resist composition comprising the carboxylate according to claim 1, an acid generator and a resin having an acid-labile group.
 7. The resist composition according to claim 6, wherein the acid generator includes a salt represented by formula (B1):

wherein, in formula (B1), Q^(b1) and Q^(b2) each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms, L^(b1) represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, —CH₂— included in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—, and a hydrogen atom included in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and —CH₂— included in the alicyclic hydrocarbon group may be replaced by —O—, —SO₂— or —CO—, and Z1⁺ represents an organic cation.
 8. The resist composition according to claim 6, wherein the resin having an acid-labile group includes at least one selected from the group consisting of a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2):

wherein, in formula (a1-0), formula (a1-1) and formula (a1-2), L^(a01), L^(a1) and L^(a2) each independently represent —O— or*—O—(CH₂)_(k1)—CO—C—, k1 represents an integer of 1 to 7, and * represents a bonding site to —CO—, R^(a01), R^(a4) and R^(a5) each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, R^(a02), R^(a03) and R^(a04) each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group obtained by combining these groups, R^(a6) and R^(a7) each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these groups, m1 represents an integer of 0 to 14, n1 represents an integer of 0 to 10, and n1′ represents an integer of 0 to
 3. 9. The resist composition according to claim 6, wherein the resin having an acid-labile group includes a structural unit represented by formula (a2-A):

wherein, in formula (a2-A), R^(a50) represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, R^(a51) represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group, A^(a50) represents a single bond or *—X^(a51)-(A^(a52)-X^(a52))_(nb)—, and * represents a bonding site to carbon atoms to which —R^(a50) is bonded, A^(a52) represents an alkanediyl group having 1 to 6 carbon atoms, X^(a51) and X^(a52) each independently represent —O—, —CO—O— or —O—CO—, nb represents 0 or 1, and mb represents an integer of 0 to 4, and when mb is an integer of 2 or more, a plurality of R^(a51) may be the same or different from each other.
 10. A method for producing a resist pattern, which comprises: (1) a step of applying the resist composition according to claim 6 on a substrate, (2) a step of drying the applied resist composition to form a composition layer, (3) a step of exposing the composition layer, (4) a step of heating the exposed composition layer, and (5) a step of developing the heated composition layer. 